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

Abstract

The invention discloses a programmable deformation and oxygen production magnetic drive soft robot and a preparation method thereof, and belongs to the technical field of composite materials and photocatalysis. And compounding hard magnetic particles (T-NdFeB) of which the surfaces are modified into kappa-carrageenan / polyacrylamide (KC / PAm) hydrogel through a free radical polymerization process to obtain the magnetic driving module. And the modules are flexibly assembled into a soft robot with a complex geometrical shape and magnetization distribution by utilizing a self-healing process among the modules, so that the soft robot can realize various programmable deformations. In addition, a Ru-Bi2CrO6 photocatalyst is obtained by doping a Ru element into Bi2CrO6, the Ru-Bi2CrO6 photocatalyst is compounded into KC / PAm hydrogel to construct a functional module capable of generating oxygen, the functional module and a magnetic driving module are further assembled into a magnetic oxygen-generating soft robot, and the purpose of stably and flexibly supplying oxygen to a water environment is achieved.

Description

Technical Field

[0001] The invention belongs to the technical field of composite materials and photocatalytic materials, and in particular relates to a magnetically driven soft robot capable of programmable deformation and oxygen production and a preparation method thereof. Background Art

[0002] The continued decline in oxygen in the world's oceans and freshwater bodies threatens productivity, biodiversity, and biogeochemical cycles. Most aquatic environments, from oceans to lakes and home fish tanks, face the need to increase oxygen levels. Compared to the use of oxygen supply equipment that causes great disturbance to the water body and consumes high energy, photocatalysis technology is widely regarded as an energy-saving method. However, the application of photocatalysts in actual water environments faces many limitations and challenges, such as the reliance on stirring to assist catalysis and the difficulty of recycling. Therefore, in order to achieve the goal of continuous oxygen supply to water bodies, how to assist photocatalysts to produce oxygen stably and efficiently has become the key.

[0003] The development of drivable soft robots provides a new possibility to achieve this goal. By compounding photocatalysts into drivable soft robots, it is not only possible to prevent the aggregation of catalysts, but also to use the robot's autonomous mobility to provide a stable and efficient oxygen supply to the water body, thereby achieving the purpose of oxygenating the target waters.

[0004] At present, various types of drivable soft robots have shown great application potential in the fields of environmental governance and drug delivery due to their excellent controllability and flexibility. Among these various driving methods, magnetically driven soft robots have gradually attracted attention due to their unique advantages such as remote control, no fuel consumption, programmability and easy recycling. This magnetically 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 easily recovered from water. Therefore, the development of magnetically driven soft robots provides new possibilities and directions for solving the problem of oxygenation in specific water bodies. At present, a variety of advanced methods and manufacturing technologies have been developed to prepare magnetically driven soft robots. For example, Kim et al. used direct ink writing technology (3D printing technology) to prepare magnetically responsive materials with complex magnetization distribution to achieve predetermined shape deformation (Nature 2018,558,274). However, the magnetization of the above method is coupled with the manufacturing process, which has high requirements for equipment and is also difficult to integrate other functions (for example, oxygen production in water). At the same time, developing and manufacturing programmable magnetically driven soft robots and conveniently realizing functional integration is still a huge challenge in this field. Summary of the invention

[0005] In view of the above problems, the purpose of the present invention is to provide a method for preparing a magnetically driven soft robot with programmable deformation and oxygen production, by compounding hard magnetic T-NdFeB into κ-carrageenan / polyacrylamide (KC / PAm) hydrogel to prepare a magnetic hydrogel with self-healing ability, namely a magnetic drive module, adding ruthenium-doped bismuth chromate catalyst (Ru-Bi2CrO6) to κ-carrageenan / polyacrylamide hydrogel to prepare a functional module, and flexibly assembling the two into a magnetic soft robot with complex geometry and magnetization distribution, so as to solve the problems of uncontrollable and difficult recycling of photocatalysts in the prior art, and difficulty in programming and functional integration of magnetically driven soft robots. The robot prepared by the method of the present invention can display a variety of programmable deformation modes under the drive of a magnetic field, and at the same time achieves the purpose of stably and flexibly providing oxygen to the target waters.

[0006] In view of the above purpose, the present invention first provides a method for preparing a programmable deformable magnetically driven soft robot, comprising the following steps:

[0007] (1) NdFeB pretreatment: NdFeB micron particles, 3-(trimethoxysilyl)propyl acrylate (TMSPMA) and ethanol were mixed and stirred, washed with deionized water after the reaction, and then dried to obtain NdFeB micron particles with TMSPMA modified on the surface, which were recorded as T-NdFeB;

[0008] (2) Preparation of carrageenan solution: mixing carrageenan and deionized water, heating and stirring until the carrageenan is completely dissolved to obtain a carrageenan solution;

[0009] (3) Preparation of T-NKP hydrogel: Add the T-NdFeB micron particles obtained in step (1) to the carrageenan solution obtained in step (2), stir evenly, and obtain a dispersion; add acrylamide, N,N'-methylenebisacrylamide, potassium chloride, and ammonium persulfate to the dispersion in sequence until they are completely dissolved, and obtain a prepolymer solution; pour the prepolymer solution into a mold for polymerization, and transfer it to a low temperature environment for a period of time after the polymerization is completed. The obtained hydrogel is T-NdFeB / KC / PAm hydrogel, referred to as T-NKP hydrogel;

[0010] (4) Preparation of a programmable deformable magnetically-actuated soft robot: The T-NKP hydrogel obtained in step (3) is magnetized using a magnetizer to obtain a magnetically-actuated module. The cut surfaces of the magnetically-actuated module are brought into contact with each other, sealed and treated in a hot water bath. The module is taken out and placed in a low-temperature environment to obtain a programmable deformable magnetically-actuated soft robot.

[0011] In one embodiment of the present invention, in step (1), the mass of NdFeB micron particles is 1-10% of the total liquid mass, preferably 1-5%, the volume of TMSPMA is 2-10% of the ethanol volume, more preferably 3-8%, the stirring time is 12-36h, the drying time is 5-10h, and the drying temperature is 40-70°C.

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

[0013] In one embodiment of the present invention, in step (3), the temperature of the carrageenan solution is first adjusted to 50-65° C., and then T-NdFeB micron particles are added thereto, and the mass of the added T-NdFeB micron particles is 2-15% of the total mass of the carrageenan solution.

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

[0015] In one embodiment of the present invention, in step (3), the polymerization temperature is 45-70°C, the time is 0.5-6h, the low temperature environment is 0-20°C, preferably 0-10°C, and the placement time is 0.1-3h.

[0016] In one embodiment of the present invention, in step (4), the temperature of the hot water bath is 70-95°C, the time is 0.1-5h, the low temperature environment is 0-20°C, and the placement time is 0.1-3h.

[0017] The invention also discloses a programmable deformable magnetically driven soft robot prepared according to the method.

[0018] The present invention also discloses a method for preparing a magnetically driven soft robot capable of programmable deformation and oxygen production, comprising the following steps:

[0019] S1. Preparation of 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 functional modules: adding a catalyst to the carrageenan solution obtained in step (1), stirring evenly to obtain a dispersion, adding acrylamide, N,N'-methylenebisacrylamide, potassium chloride and ammonium persulfate to the dispersion until they are completely dissolved to obtain a prepolymer solution; pouring the prepolymer solution into a mold for polymerization, and transferring it to a low temperature environment for a period of time after the polymerization is completed, and obtaining a hydrogel as a functional module;

[0021] S3. The cut surfaces of the magnetic drive module and the functional module are brought into contact with each other, sealed and treated in a hot water bath, taken out and placed in a low-temperature environment to obtain a magnetically driven soft robot OGR with programmable deformation and oxygen production.

[0022] In one embodiment of the present invention, in step S1, the carrageenan is κ-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 0.1-3 h.

[0023] In one embodiment of the present invention, the catalyst described in step S2 is Ru-Bi2CrO6, and the preparation method of the Ru-Bi2CrO6 catalyst is: dissolving bismuth nitrate and potassium chromate in a nitric acid solution, adjusting the pH value of the solution to 0.8-1.4 with aqueous ammonia under stirring, collecting the solid after hydrothermal reaction, washing and drying to obtain Bi2CrO6; adding the obtained Bi2CrO6 and ruthenium trichloride to ethylene glycol together, reacting for a period of time under stirring; after the reaction, filtering and drying, and then calcining in a muffle furnace, the obtained sample is Ru-Bi2CrO6.

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

[0025] In one embodiment of the present invention, 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 one embodiment of the present invention, in step S2, when preparing the dispersion, the temperature of the carrageenan solution is first adjusted to 50-65°C, and then Ru-Bi2CrO6 is added, and the amount of Ru-Bi2CrO6 added is 1%-5% of the mass of the carrageenan solution.

[0027] In one embodiment of the present invention, in step S2, when preparing the prepolymer solution, the amount of acrylamide added is 4 to 12 times the mass of carrageenan, the amount of N,N'-methylenebisacrylamide added is 0.02 to 1% of the mass of acrylamide, the amount of potassium chloride added is 3 to 12% of the mass of carrageenan, and the amount of ammonium persulfate added is 0.5 to 2% of the mass of acrylamide.

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

[0029] In one embodiment of the present invention, in step S3, the hot water bath temperature is 70-95°C, the time is 0.1-5h, the low temperature environment is 0-20°C, and the placement time is 0.1-5h.

[0030] The present invention also provides a magnetically driven soft robot with programmable deformation and oxygen production, which is prepared according to the above method.

[0031] The present invention also provides the application of the above-mentioned magnetically driven soft robot with programmable deformation and oxygen production in the field of deformable actuators or photocatalysis, including photocatalytic oxygen production.

[0032] Beneficial effects:

[0033] 1. The present invention uses carrageenan with thermoreversible phase change behavior to prepare a double network hydrogel with self-healing properties, which can use its self-healing properties to freely assemble magnetic drive modules into larger shapes and achieve a variety of programmable deformations. The T-NKP-1.5 hydrogel obtained by combining T-NdFeB micron particles with hydrogel has good mechanical properties, and its elongation at break reaches 337%.

[0034] 2. The present invention composites the photocatalyst into the magnetically driven soft robot to assist the photocatalyst in achieving uniform dispersion, while improving the adaptability and flexibility of the photocatalyst.

[0035] 3. The strategy of realizing module assembly by utilizing the self-healing process proposed in the present invention can be extended to other materials, facilitating the integration of functional materials into drivable soft robots, thereby expanding the application scope of soft robots.

[0036] 4. The preparation process of the programmable deformation and oxygen-producing magnetically driven soft robot designed by the present invention includes free radical polymerization and hydrothermal method. The preparation method is simple and explores an effective method for preparing programmable multifunctional soft robots. At the same time, it provides an effective way to develop oxygen-producing soft robots and solve the problem of decreased oxygen content in water bodies, and has great commercial prospects.

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

[0038] Figure 1 It is a schematic diagram of a method for preparing a magnetically driven soft robot with programmable deformation in the present invention;

[0039] Figure 2 These are stress-strain curves of several T-NKP hydrogels and KC / PAm hydrogels prepared in Example 1 and Comparative Examples 1 to 3 of the present invention;

[0040] Figure 3 This is the self-healing process of the T-NKP-1.5 hydrogel prepared in Example 1 of the present invention;

[0041] Figure 4 The curves of the bending angle of the hydrogels prepared in Example 1 and Comparative Examples 2 to 3 of the present invention under a magnetic field of 18 mT as a function of the mass of the added T-NdFeB;

[0042] Figure 5 is a schematic diagram of the assembly of the T-NKP-1.5 hydrogel prepared in Example 1 of the present invention and a deformation photograph of the magnetically driven soft robot obtained after the assembly under a magnetic field;

[0043] Figure 6 It is the performance diagram of photocatalytic oxygen production of Bi2CrO6, Ru-Bi2CrO6 and OGR prepared by Comparative Examples 4-5 and Example 2 respectively;

[0044] Figure 7 This is a motion trajectory diagram of the OGR prepared in Example 2 driven by a magnetic field. DETAILED DESCRIPTION

[0045] The present invention will be further described below in conjunction with specific embodiments, and it should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope limited by the appended claims of the application.

[0046] Unless otherwise specified, the materials used in the embodiments and comparative examples of the present invention are all purchased from the market. Unless otherwise specified, the tests on the performance of the hydrogel and the robot are all conducted using conventional testing methods.

[0047] Example 1

[0048] A method for preparing a programmable deformable magnetically driven soft robot comprises the following steps:

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

[0050] (2) 0.4 g of κ-carrageenan was added to 15 mL of deionized water, and the mixture was stirred at 80° C. for 2 h until it was completely dissolved; the temperature of the solution was then adjusted to 60° C., 1.5 g of T-NdFeB obtained in step (1) was added, and the mixture was stirred for 30 min, and 3.2 g of acrylamide, 1.6 mg of N,N'-methylenebisacrylamide, 24 mg of potassium chloride, and 32 mg of ammonium persulfate were added in sequence until they were completely dissolved to obtain a prepolymer solution; the prepolymer solution was then poured into a mold for polymerization at a polymerization temperature of 60° C. and a reaction time of 5 h; the sample obtained by polymerization was finally transferred to a 4° C. environment and placed for 1 h. The prepared hydrogel was recorded as T-NKP-1.5 hydrogel ("1.5" represents the mass of the added T-NdFeB microparticles);

[0051] (3) The T-NKP-1.5 hydrogel can be magnetized to obtain a magnetically driven module; the cut surfaces of multiple magnetic modules are contacted together, and then sealed in a polyethylene bag and immersed in a hot water bath at 80°C for 1 hour; then it is taken out and placed in an environment of 4°C for 30 minutes. The assembled (self-healing) sample obtained is a programmable deformable magnetically driven soft robot.

[0052] The present invention utilizes the ability of κ-carrageenan to undergo a thermally reversible phase change to make KC / PAm hydrogel have self-healing properties. During preparation, magnetic micron particles (T-NdFeB) are compounded into KC / PAm hydrogel to obtain a magnetic drive module. The magnetic drive module is freely assembled using its self-healing ability, and a programmable deformable magnetic soft robot is successfully obtained, which can achieve multiple deformations in water.

[0053] Figure 1 Schematic diagram of the preparation method of a programmable deformable magnetically driven soft robot. Ammonium persulfate is used as an initiator to cause free radical polymerization of acrylamide, N,N'-methylenebisacrylamide and T-NdFeB in the prepolymer solution to obtain a single network. Then, the temperature of the hydrogel is lowered to make K + The T-NKP-1.5 hydrogel obtained by polymerization has good mechanical properties, and its elongation at break reaches 337% ( Figure 2 ). T-NKP-1.5 hydrogel undergoes Figure 3 After the healing process, the two hydrogels can be tightly connected together and can withstand a certain degree of stretching. Figure 4 The results show that the bending angle of T-NKP-1.5 hydrogel under a magnetic field of 18 mT is close to 90°, indicating its good magnetic responsiveness. The assembled series of magnetically driven soft robots can achieve multiple deformation modes under a magnetic field ( Figure 5 ).

[0054] Comparative Example 1

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

[0056] Mechanical properties test results ( Figure 2 ) showed that NKP-1.5 hydrogel had a lower elongation at break (203%) than T-NKP-1.5 hydrogel, and its mechanical properties were worse than those of 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 obtained hydrogel is recorded as T-NKP-2.

[0059] Mechanical properties test results ( Figure 2 ) showed that T-NKP-2 hydrogel had a lower elongation at break (25%) than T-NKP-1.5 hydrogel, and its mechanical properties were poorer.

[0060] Comparative Example 3

[0061] The difference between Comparative Example 3 and Example 1 is that the amount of T-NdFeB added in step (2) is replaced from 1.5 g to 1.0 g, and the obtained hydrogel is recorded as T-NKP-1.

[0062] Figure 4 It shows 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 T-NKP hydrogel, the increase of T-NdFeB content will reduce the mechanical properties of T-NKP hydrogel.

[0064] Example 2

[0065] A method for preparing a magnetically driven soft robot capable of programmable deformation and oxygen production comprises the following steps:

[0066] (1) 2 mmol of bismuth nitrate pentahydrate and 1 mmol of potassium chromate were dissolved in 30 mL of 2 M nitric acid solution, and the pH value of the solution was adjusted to 1 with aqueous ammonia under stirring; the solution was then transferred to a hydrothermal reactor for hydrothermal reaction at a temperature of 180° C. for 10 h; the obtained sample was washed with deionized water and dried to obtain the final product Bi2CrO6;

[0067] (2) 0.0995 g of Bi2CrO6 and 1 mg of ruthenium trichloride were added to 30 mL of ethylene glycol and stirred at 180°C for 10 h, followed by filtration and drying to obtain a sample; the sample was then transferred to a muffle furnace and heated to 350°C and maintained for 3 h to obtain Ru-Bi2CrO6;

[0068] (3) 0.4 g of κ-carrageenan was added to 15 mL of deionized water, and the mixture was stirred at 80 ° C for 2 h until it was completely dissolved. The temperature of the solution was then adjusted to 60 ° C, 0.5 g of Ru-Bi2CrO6 obtained in step (2) was added, and the mixture was stirred for 30 min. 3.2 g of acrylamide, 1.6 mg of N,N'-methylenebisacrylamide, 24 mg of potassium chloride and 32 mg of ammonium persulfate were added in sequence until they were completely dissolved to obtain a prepolymer solution. The prepolymer solution was then quickly poured into a mold for polymerization at a polymerization temperature of 60 ° C and a reaction time of 5 h. The sample obtained by polymerization was finally transferred to a 4 ° C environment and placed for 1 h. The prepared hydrogel was a functional module.

[0069] (4) The T-NKP-1.5 hydrogel obtained in Example 1 is magnetized to obtain a magnetic drive module. A magnetic drive module is brought into contact with a cut surface of a functional module obtained in step (3), and then sealed in a polyethylene bag and immersed in a hot water bath at 80° C. for 1 h; then taken out and placed at 4° C. for 30 min. The assembled (self-healed) sample finally obtained is OGR (the actual OGR sample is shown in FIG. Figure 7 shown);

[0070] In the photocatalytic test, 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 the air; a 300 W xenon lamp was used to irradiate the photocatalytic system, and the generated oxygen was detected using gas chromatography. Photocatalytic test results ( Figure 6 ) showed that the photocatalytic efficiency of OGR reached 389.1 μmol g -1 h -1 , and can maintain a photocatalytic efficiency comparable to that of powder photocatalyst (Ru-Bi2CrO6).

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

[0072] Comparative Example 4

[0073] The difference between Comparative Example 4 and Example 2 is that steps (3) and (4) are omitted and Ru-Bi2CrO6 powder is directly used for photocatalytic testing.

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

[0075] Comparative Example 5

[0076] The difference between Comparative Example 5 and Example 2 is that step (2) is omitted and Ru-Bi2CrO6 in step (3) is replaced by Bi2CrO6.

[0077] Photocatalytic test results ( Figure 6) showed that Bi2CrO6 photocatalyst had a lower oxygen generation efficiency (148.4 μmol g -1 h -1 ), indicating that Ru doping can significantly improve the efficiency of photocatalytic oxygen production of the photocatalyst.

[0078] The embodiments provided above are not intended to limit the scope of the present invention, and the steps described are not intended to limit the execution order thereof. Those skilled in the art may make obvious improvements to the present invention in combination with existing common knowledge, which also fall within the scope of protection defined by the claims of the present invention.

Claims

1. A method for preparing a programmable deformable magnetically driven soft robot, characterized in that: The steps include: (1) NdFeB pretreatment: NdFeB micron particles, 3-(trimethoxysilyl)propyl acrylate (TMSPMA) and ethanol were mixed and stirred for 12-36 hours. After the reaction, the particles were washed with deionized water and then dried at 40-70°C for 5-10 hours to obtain NdFeB micron particles with TMSPMA modified on the surface, which were denoted as T-NdFeB. (2) Preparation of carrageenan solution: mixing carrageenan and deionized water, heating and stirring until the carrageenan is completely dissolved to obtain a carrageenan solution; (3) Preparation of T-NKP hydrogel: Add the T-NdFeB micron particles obtained in step (1) to the carrageenan solution obtained in step (2), stir evenly, and obtain a dispersion; add acrylamide, N,N'-methylenebisacrylamide, potassium chloride, and ammonium persulfate to the dispersion in sequence until they are completely dissolved, and obtain a prepolymer solution; pour the prepolymer solution into a mold for polymerization, and after the polymerization, transfer to an environment of 0 to 20°C and place for 0.1 to 3 hours. The obtained hydrogel is T-NdFeB / KC / PAm hydrogel, referred to as T-NKP hydrogel; (4) Preparation of a programmable deformable magnetically-actuated soft robot: The T-NKP hydrogel obtained in step (3) is magnetized using a magnetizer to obtain a magnetically-actuated module. The cut surfaces of the magnetically-actuated module are contacted together, sealed, and treated in a hot water bath at 70 to 95° C. for 0.1 to 5 h. After being taken out, the module is placed in an environment at 0 to 20° C. for 0.1 to 3 h to obtain a programmable deformable magnetically-actuated soft robot.

2. The preparation method according to claim 1, characterized in that: In step (1), the mass of NdFeB micron particles is 1-10% of the mass of the total liquid, and the volume of TMSPMA is 2-10% of the volume of ethanol.

3. The preparation method according to claim 1, characterized in that: In step (2), the carrageenan is κ-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 0.1-3 h.

4. The preparation method according to claim 1, characterized in that: In step (3), the temperature of the carrageenan solution is first adjusted to 50-65° C., and then T-NdFeB micron particles are added thereto, wherein the mass of the added T-NdFeB micron particles is 2-15% of the total mass of the carrageenan solution. When preparing the prepolymer 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. The polymerization temperature is 45-70° C. and the time is 0.5-6 h.

5. A programmable deformable magnetically driven soft robot prepared according to the preparation method according to any one of claims 1 to 4.

6. A method for preparing a magnetically driven soft robot with programmable deformation and oxygen production, characterized in that: The following steps are involved: S1. Preparation of carrageenan solution: Mix κ-carrageenan and deionized water, heat to 60-90° C., and stir for 0.1-3 h until the κ-carrageenan is completely dissolved to obtain a carrageenan solution; S2, preparation of functional modules: adding a catalyst to the carrageenan solution obtained in step (1), stirring evenly to obtain a dispersion, adding acrylamide, N,N'-methylenebisacrylamide, potassium chloride and ammonium persulfate to the dispersion until they are completely dissolved to obtain a prepolymer solution; pouring the prepolymer solution into a mold for polymerization, and transferring it to a low temperature environment for a period of time after the polymerization is completed, and obtaining a hydrogel as a functional module; S3. The magnetic drive module obtained in step (4) of claim 1 and the cut surface of the functional module obtained in step S2 are brought into contact with each other, sealed and treated in a hot water bath at 70 to 95°C for 0.1 to 5 hours, and then placed in an environment of 0 to 20°C for 0.1 to 3 hours to obtain a magnetically driven soft robot OGR that can be programmably deformed and produce oxygen.

7. The preparation method according to claim 6, characterized in that: The mass fraction of carrageenan in the carrageenan solution described in step S2 is 1-5%, and the catalyst is Ru-Bi2CrO6. The preparation method of the Ru-Bi2CrO6 catalyst is as follows: dissolving bismuth nitrate and potassium chromate in a nitric acid solution, adjusting the pH value of the solution to 0.8-1.4 with ammonia water under stirring, collecting the solid after hydrothermal reaction, washing and drying to obtain Bi2CrO6; adding the obtained Bi2CrO6 and ruthenium trichloride to ethylene glycol together, reacting for a period of time under stirring; filtering and drying after the reaction, and then calcining in a muffle furnace to obtain a sample of Ru-Bi2CrO6; Wherein, when preparing Bi2CrO6, the molar ratio of bismuth nitrate to potassium chromate is 1-4:1, the concentration of the nitric acid solution is 1-3 mol / L, the sum of the concentrations of bismuth nitrate and potassium chromate in the nitric acid solution is 0.05-0.2 mol / L, the temperature of the hydrothermal reaction is 180°C, and the time is 3-12h.

8. The preparation method according to claim 7, characterized in that: When preparing Ru-Bi2CrO6, the mass ratio of ruthenium trichloride to 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.

9. The preparation method according to claim 6, characterized in that: In step S2, when preparing the dispersion, first adjust the temperature of the carrageenan solution to 50-65°C, then add Ru-Bi2CrO6, the amount of Ru-Bi2CrO6 added is 1%-5% of the mass of the carrageenan solution, when preparing the prepolymer solution, the amount of acrylamide added is 4-12 times the mass of carrageenan, the amount of N,N'-methylenebisacrylamide added is 0.02-1% of the mass of acrylamide, the amount of potassium chloride added is 3-12% of the mass of carrageenan, the amount of ammonium persulfate added is 0.5-2% of the mass of acrylamide, the polymerization temperature is 45-70°C, the time is 0.5-6h, the low temperature environment is 0-20°C, preferably 0-10°C, and the placement time is 0.1-3h.

10. A magnetically driven soft robot with programmable deformation and oxygen production obtained by the preparation method according to any one of claims 6 to 9.

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