A porous active material surface biomimetic modification layer and a preparation method thereof

Abstract

The application provides a porous active material surface biomimetic modification layer and a preparation method thereof, and comprises the following steps: S1. preparing an active metal porous material, pretreating the active metal porous material, and waiting for use; S2. mixing lysozyme and a cell buffer to obtain a lysozyme type solution; mixing the cell buffer and a disulfide reducing agent in the same proportion to obtain a disulfide reducing agent solution; mixing the lysozyme type solution and the disulfide reducing agent solution in equal volumes to obtain a lysozyme mineralization biomimetic solution, and waiting for use; S3. immersing the active metal porous material into the lysozyme mineralization biomimetic solution, incubating, taking out, and placing into a circulating pump for circulating treatment, cleaning and drying, so that the porous active material surface biomimetic modification layer is obtained. The porous active material surface biomimetic modification layer prepared by the preparation method has excellent antibacterial property, bone integration promoting property and good mechanical strength, can realize controllable degradation of the porous alloy material, and is suitable for bone implants.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of alloy coating preparation process, and particularly relates to a porous active material surface biomimetic modification layer and a preparation method thereof. BACKGROUND

[0002] Degradable active metal materials, such as titanium alloy, magnesium alloy, zinc alloy, iron-based alloy, etc., have been widely favored by researchers in recent years due to their advantages of good strength and toughness, beneficial degradation products to human body, and no need for secondary surgery to remove. Although the elastic modulus (40-50 GPa) of the actual body is closer to the human compact bone (1-30 GPa), it still needs to be made into a porous structure to effectively reduce its elastic modulus to prevent the occurrence of stress shielding and other problems. Selective laser melting technology (Selective Laser Melting, SLM) as an effective means for preparing complex gradient porous structures has been widely used in the field of orthopedic medical devices such as large bone defects, stents, intervertebral fusion cages, etc. However, the degradable materials represented by titanium alloy and magnesium alloy have poor corrosion resistance, and the degradation rate in the physiological environment will be faster. The design of the porous structure increases the specific surface area of the implant, which further increases the corrosion rate of the implant, leading to problems such as premature failure of the bone implant, local hydrogen accumulation and alkaline microenvironment, which restricts the further application of degradable active metals in the fields of tissue engineering scaffolds, cardiovascular stents, bone implant devices and other biomedical fields.

[0003] For corrosion-resistant active metal materials, traditional surface modification methods such as micro-arc oxidation are often used for overall protection. However, due to the more complex structure of porous materials compared to solids, it is difficult to use conventional methods for surface modification. Although Chinese patents CN 118563386A "Preparation method and application of intelligent self-repairing coating based on new sealing treatment micro-arc oxidation coating" and CN 116618273A "Method for preparing composite biological coating on magnesium alloy micro-arc oxidation coating" both mention post-treatment of micro-arc oxidation coating to prepare composite coating, and micro-arc oxidation (MAO) technology, as a method of generating a ceramic film layer on the surface of an alloy in situ through high-temperature and high-pressure arc discharge, has been widely used in the field of surface modification in recent years. However, the coating prepared by micro-arc oxidation has a large number of micron-sized pores and defects on the outside, increasing the opportunity for corrosion of corrosive ions and microorganisms, and weakening the corrosion resistance of the MAO film. Therefore, this technology still needs to be combined with other means to prepare a composite coating to enhance its corrosion resistance. Other methods such as spraying, surface plating, and chemical conversion still have issues such as complex processing, insufficient wettability, and limited bonding strength. In addition, the coatings prepared at the present stage do not have the growth environment required by bone tissue, and are only prepared for the purpose of achieving wear-resistant and corrosion-resistant coatings on the surface of the substrate, without considering the time-dependent growth effect of three-dimensional bone tissue.

[0004] Chinese patent CN115120783A "Porous titanium-based antibacterial active material and preparation method and application" discloses a porous titanium-based antibacterial active material including a porous titanium-based alloy material and a bioactive coating. A tantalum coating and a silver-containing hydroxyapatite layer are prepared using physical vapor deposition technology. The hydroxyapatite layer prepared by cold spraying has high crystallinity and is not easily degraded. However, the coating of the porous titanium-based antibacterial active material has limited bonding strength with the material, the strength is not high, and the antibacterial effect is low, and the bioactivity needs to be further improved.

[0005] Therefore, it is of great significance to develop a high-bonding-strength surface biomimetic modification layer for porous active materials that can effectively improve the electrochemical performance of lithium-ion batteries, as well as a preparation method and application thereof. SUMMARY

[0006] In view of the problems of existing porous active materials, such as limited bonding strength between the coating and the material, low strength, and low antibacterial effect, and the need for further improvement of bioactivity, the present application provides a porous active material surface biomimetic modification layer and a preparation method thereof. By inducing a hydroxyapatite coating on the surface of the active metal porous material, a porous active material surface biomimetic modification layer is obtained, which has excellent antibacterial properties, bone integration properties, and good mechanical strength, can achieve controlled degradation of the porous alloy material, and is suitable for bone implants.

[0007] To achieve the above object, the technical scheme adopted by the present application is:

[0008] A preparation method of a biomimetic modified layer on the surface of a porous active material, comprising the following steps:

[0009] S1. An active metal porous material with a pore size of 400-2000 mu m and a porosity of 40-80% is prepared by SLM, and is pretreated, the pretreatment including surface sand blasting, ultrasonic cleaning, repeating the ultrasonic cleaning step 3-5 times, drying, and waiting for use;

[0010] S2. Lysozyme is mixed with a cell buffer to obtain a lysozyme type solution; a cell buffer and a reducing agent are mixed in the same proportion to adjust the pH to 5-6.8 to obtain a reducing agent solution; the lysozyme type solution and the reducing agent solution are mixed in equal volumes to obtain a lysozyme mineralization biomimetic solution, and are waiting for use;

[0011] S3. The active metal porous material obtained in S1 is immersed in the lysozyme mineralization biomimetic solution obtained in S2, incubated, taken out and placed in a circulating pump containing the lysozyme mineralization biomimetic solution obtained in S2, and is treated at a circulation rate of 0.5-2 mL / min for 15-20 min, repeated 3-5 times, washed, and dried to obtain the biomimetic modified layer on the surface of the porous active material.

[0012] Further, the active metal porous material in S1 is one or more of titanium-based material, magnesium-based material, iron-based material, and zinc-based material; and the porous structure in the active metal porous material in S1 is one or more of body-centered cubic, face-centered cubic, regular octahedron, and triply minimal surface.

[0013] Further, the cleaning medium in the ultrasonic cleaning in S1 is one or more of 5-20 vol.% perchloric acid alcohol, 3-5 vol.% nitric acid alcohol, and 10-20 vol.% dilute hydrochloric acid, the vibration frequency is 10-20 kHz, and the ultrasonic time is 10-20 min.

[0014] The vibration frequency of the ultrasonic treatment is preferably 10-20 kHz, and the ultrasonic time is 10-20 min, and the above steps are repeated at least 3 times, so that the adhesive powder and corrosion peeling products in the porous material are completely flushed out, and the active metal material is covered with a relatively dense oxide film, which will not be peeled off in a large area due to subsequent processing, and is beneficial to improve the formation effect of the biomimetic modified layer on the surface of the porous active material.

[0015] Further, the drying in S1 is blowing dry by using a high-pressure jet of inert gas, and the inert gas is 99.999 vol.% high-purity argon and / or nitrogen.

[0016] The application preferably adopts 99.999 vol.% high-purity argon and / or nitrogen to blow dry the active metal porous material as a whole, avoids bringing the corrosion liquid into the active metal porous material, avoids the possible large-area oxidation phenomenon of the active metal porous material, and further affects the formation effect of the biomimetic modified layer on the surface of the porous active material.

[0017] Further, the cell buffer solution in S2 comprises one or more of 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid, N-(2-acetamido)-2-aminoethanesulfonic acid, and 3-(N-morpholino)propanesulfonic acid; and the pH of the cell buffer solution is 7-8.

[0018] The application preferably controls the pH of the cell buffer solution to be between 7 and 8, that is, the entire liquid environment needs to be stabilized in a neutral or weakly alkaline environment, so as to facilitate the biomimetic mineralization effect of the subsequent action on the surface of the active metal porous material, and promote the surface to grow a hydroxyapatite protective layer more easily.

[0019] Further, the reducing agent in S2 is one or more of tris(2-carboxyethyl)phosphine hydrochloride, dithiothreitol, and tris(3-hydroxypropyl)phosphine.

[0020] The application preferably uses a reducing agent for reducing disulfide bonds in protein chemistry and proteomics research, so as to prevent the intramolecular or intermolecular disulfide bonds formed between cysteines in the protein, and promote the biomimetic mineralization effect of the action on the surface of the active metal porous material to grow a hydroxyapatite protective layer.

[0021] Further, the adjustment of the pH to 5-6.8 in S2 is adjusted by a strong alkaline solvent; and the strong alkaline solvent is one or more of NaOH, KOH, and Ca(OH)2.

[0022] The application preferably uses NaOH, KOH, and Ca(OH)2, etc., which are elements commonly contained in organisms, so as to avoid introducing excess ions that are not conducive to the growth of organisms during the treatment process, thereby affecting the formation effect of the biomimetic modified layer on the surface of the porous active material.

[0023] Further, the incubation in S3 is incubation in a thermostat, the temperature is 18-37℃, the relative humidity is 45-60%, and the incubation time is 1.5-3h.

[0024] The application preferably uses a thermostat with a temperature of 18-37℃, a relative humidity of 45-60%, and an incubation time of 1.5-3h, so as to prevent the lysozyme mineralization biomimetic solution from being insufficiently biomimetic mineralized due to too short storage time, and to prevent the lysozyme mineralization biomimetic solution from being placed for too long time to cause moisture absorption, and further cause problems such as concentration reduction or even failure, thereby affecting the formation effect of the biomimetic modified layer on the surface of the porous active material.

[0025] Further, the cleaning in S3 is to clean the inside and surface of the porous material by using high-purity organic solvent; the high-purity organic solvent is one or more of anhydrous ethanol, dimethyl carbonate and diethyl carbonate; the drying in S3 is to blow the residual solution and salt on the surface of the active metal porous material by using inert gas; the inert gas is 99.999 vol.% high-purity argon and / or nitrogen.

[0026] Preferably, the high-purity organic solvent is one or more of anhydrous ethanol, dimethyl carbonate and diethyl carbonate, which avoids leaving possible harmful substances in the inside of the porous structure and produces toxic side effects on the organism after implantation.

[0027] Another object of the present application is to provide a surface biomimetic modification layer of a porous active material.

[0028] A surface biomimetic modification layer of a porous active material is prepared by the method for preparing a surface biomimetic modification layer of a porous active material according to any one of the preceding items.

[0029] Compared with the prior art, the present application has the following advantages and beneficial effects:

[0030] (1) The method for preparing a surface biomimetic modification layer of a porous active material is simple and fast, and is suitable for various active degradable metal materials; the in-situ hydroxyapatite coating formed by the method is not only tightly combined with the substrate, but also can obtain a uniform surface biomimetic modification layer on the inner and outer surfaces of different types of active metal porous materials.

[0031] (2) The surface biomimetic modification layer of a porous active material prepared by the present application forms a protective film with continuous film layer and uniform thickness (about 10 μm) in the preparation process, which not only improves the strength and hardness, but also improves the corrosion resistance, so that the degradation rate of the surface biomimetic modification layer of a porous active material in the actual service process is greatly reduced.

[0032] (3) The hydroxyapatite biomimetic coating formed in situ on the surface of the porous active material of the porous active material surface biomimetic modification layer is prepared by mixing a lysozyme type solution and a reducing agent solution into a lysozyme mineralization biomimetic solution, the specific reducing agent in the application can be used as a chelating agent for various metal ions such as Ti, Zn, Mg and the like, and can exist stably in an alkaline or acidic solution, and can form a complex with a ring structure on the surface of the porous active material, thereby stably connecting the metal substrate surface and the hydroxyapatite layer grown in situ, obtaining a stable biomimetic mineralized hydroxyapatite nanomembrane layer formed in situ on the surface of the porous active material, which ingeniously imitates the mineralized bone tissue on the periphery of the original bone tissue, and is very suitable for the adhesion of osteoblasts on the surface; and the porous active metal scaffold formed by the SLM technology is modified on the surface to form a plurality of micro-nano holes, which promotes the further climbing of the osteoblasts, and further improves the osteointegration thereof. In combination with the Mg 2+ , Zn 2+ , Cu 1+ / Cu 2+ ion products formed after the degradation of the active metal, excellent antibacterial properties are exhibited. BRIEF DESCRIPTION OF DRAWINGS

[0033] The application is further described by using the drawings, but the embodiments in the drawings do not constitute any limitation on the application, and other drawings can be obtained by those skilled in the art without creative labor on the basis of the following drawings.

[0034] Figure 1 It is a preparation flow chart of the porous active material surface biomimetic modification layer of the application.

[0035] Figure 2 It is a micro cross-section morphology and element distribution graph of the porous active material surface biomimetic modification layer of the application.

[0036] Figure 3 It is a micro-morphology graph of the comparative example 1 of the application.

[0037] Figure 4 It is a physical graph of the comparative example 2 of the application.

[0038] Figure 5 It is a physical graph of the comparative example 3 of the application.

[0039] Figure 6 It is an internal OM morphology graph of the comparative example 4 of the application.

[0040] Figure 7 It is a physical graph of the comparative example 5 of the application.

[0041] Figure 8 It is a cell staining graph of the comparative example 6 and the example 1 of the application, the left is the comparative example 6, and the right is the example 1.

[0042] Figure 9 Cellular structure of porous active material of Example 1 and untreated porous active material. DETAILED DESCRIPTION

[0043] For the purpose of better illustrating the technical scheme, advantages and effects of the present application, the present application is further illustrated by the following examples. Obviously, the following examples are only a part of the examples of the present application, but not all the examples; it should be understood that the examples of the present application are only used to illustrate the technical effects of the present application, but not used to limit the protection scope of the present application.

[0044] The present application will be described in detail through the following examples, which do not mean any limitation to the present application. Those skilled in the art should understand that these examples are only used to illustrate the present application and not used to limit the scope of the present application. The experimental methods not specified in the following examples are usually carried out according to the conventional conditions or according to the conditions recommended by the manufacturers. Unless otherwise specified, the percentages and parts are calculated by weight. The following examples are mainly used to better understand the analysis method of the present application, and do not exhaust all the operation modes. The weight parts in the following text can represent the conventional unit of measurement in the art, such as kilograms, grams, etc., or can represent the ratio between components, such as mass or weight ratio, etc.

[0045] The raw materials in the examples can be obtained by market purchase; unless otherwise specified, the reagents, methods and equipment used in the present application are conventional reagents, methods and equipment in the technical field.

[0046] Example 1: A method for preparing a biomimetic modification layer on the surface of a porous active material, comprising the following steps:

[0047] S1. A body-centered cubic AZ91D magnesium alloy with a pore size of 550 μm and a porosity of 60% is prepared by SLM, and pretreated, which specifically includes first using a sand blasting machine to perform sand blasting treatment on the outer layer of the powder, then using 10 vol.% hydrochloric acid ethanol solution to perform ultrasonic treatment for 15 min, then taking out and immersing it in an ethanol solution and then re-performing ultrasonic vibration for 15 min, the vibration frequency is set to 15 kHz, and the above steps are repeated for 3 times, then pure argon gas with a purity of 99.999 vol.% is used to blow dry the whole, and is ready for use;

[0048] S2. 2 mg / mL lysozyme is mixed with 10 mmol / L 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES) cell buffer with pH of 7-8 to obtain a lysozyme type solution; the same component and proportion of cell buffer and 50 mL tris(2-carboxyethyl) phosphine hydrochloride (TCEP) reducing agent are mixed, and the pH is adjusted to 5.8 by 5 mol / L NaOH strong alkaline solvent to obtain a reducing agent solution; the lysozyme type solution and the reducing agent solution are taken and mixed in equal volume, and are uniformly mixed by ultrasonic vibration to obtain a lysozyme mineralization biomimetic solution, which is ready for use;

[0049] S3. The active metal porous material is fully cleaned inside and on the surface by using high-purity anhydrous ethanol, immersed in the lysozyme mineralization biomimetic solution obtained in S2, incubated in a thermostat at a temperature of 20℃ and a humidity of 55%, incubated for 2 h, taken out and placed in a circulating pump containing the lysozyme mineralization biomimetic solution obtained in S2, and treated by circulation at a rate of 0.8 mL / min for 18 min, repeated for 3 times, immersed in anhydrous ethanol solvent, and ultrasonic vibration is performed at a vibration frequency of 15 kHz, and after the residual solution inside and on the surface of the porous material is completely cleaned, the residual solution and salt on the surface of the active metal porous material are blown dry by using high-purity argon (99.999 vol.%), to obtain the biomimetic modified layer on the surface of the porous active material.

[0050] Embodiment 2: A method for preparing a biomimetic modified layer on the surface of a porous active material, comprising the following steps:

[0051] S1. A regular octahedron WE43 magnesium alloy with a pore size of 1310 μm and a porosity of 76% is prepared by SLM, and is pretreated, specifically including: first, the outer layer is sandblasted by using a sandblasting machine, then 10 vol.% hydrochloric acid ethanol solution is used for ultrasonic treatment for 15 min, then the material is immersed in ethanol solution and ultrasonic vibration is performed again for 15 min at a vibration frequency of 15 kHz, and the above steps are repeated for 3 times, and finally, the whole is blown dry by using high-purity argon with a purity of 99.999 vol.% and is ready for use;

[0052] S2. 2 mg / mL lysozyme is mixed with 10 mmol / L N-(2-acetamido)-2-aminoethanesulfonic acid (ACES) cell buffer with pH of 7-8 to obtain a lysozyme type solution; the same component and proportion of cell buffer and 50 mL dithiothreitol (DTT) reducing agent are mixed, and the pH is adjusted to 5.8 by 5 mol / L NaOH strong alkaline solvent to obtain a reducing agent solution; the lysozyme type solution and the reducing agent solution are taken and mixed in equal volume, and are uniformly mixed by ultrasonic vibration to obtain a lysozyme mineralization biomimetic solution, which is ready for use;

[0053] S3. The active metal porous material obtained in S1 is immersed in the lysozyme mineralization biomimetic solution obtained in S2, and is incubated in a thermostat at 20°C and a humidity of 55% for 2h. After being taken out, the active metal porous material is placed in a circulating pump containing the lysozyme mineralization biomimetic solution obtained in S2, and is treated at a circulation rate of 1.5mL / min for 20min, repeated 4 times. The active metal porous material is immersed in anhydrous ethanol solvent, and is ultrasonically vibrated at a vibration frequency of 15kHz. After the residual solution in the interior and on the surface of the porous material is completely cleaned, the residual solution and salt on the surface of the active metal porous material are blown dry with high-purity argon (99.999vol.%), to obtain the biomimetic modified layer on the surface of the porous active material.

[0054] Example 3: A method for preparing a biomimetic modified layer on the surface of a porous active material, comprising the following steps:

[0055] S1. A body-centered cubic pure Zn with a pore size of 550μm and a porosity of 60% is prepared by SLM, and is pretreated as follows. First, the outer layer is sanded with a sandblaster, and then is ultrasonically treated with 10vol.% hydrochloric acid ethanol solution for 15min. After being taken out, the Zn is immersed in ethanol solution and is ultrasonically vibrated again for 15min at a vibration frequency of 15kHz. The above steps are repeated 3 times. Finally, the Zn is blown dry with high-purity argon (purity 99.999vol.%), and is ready for use.

[0056] S2. 2mg / mL lysozyme is mixed with 10mmol / L 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES) cell buffer with a pH of 7-8 to obtain a lysozyme type solution. The same proportion of cell buffer and 50mL tris(2-carboxyethyl)phosphine hydrochloride (TCEP) reducing agent are mixed, and the pH is adjusted to 5.8 with 5mol / L NaOH strong alkaline solvent to obtain a reducing agent solution. The lysozyme type solution and the reducing agent solution are mixed in equal volumes, and are ultrasonically vibrated to obtain a lysozyme mineralization biomimetic solution, ready for use.

[0057] S3. The active metal porous material obtained in S1 is immersed in the lysozyme mineralization biomimetic solution obtained in S2, and is incubated in a thermostat at 20°C and a humidity of 55% for 2h. After being taken out, the active metal porous material is placed in a circulating pump containing the lysozyme mineralization biomimetic solution obtained in S2, and is treated with a circulation of 0.8mL / min for 18min, repeated for 3 times. The active metal porous material is immersed in anhydrous ethanol solvent, and is ultrasonically vibrated at a vibration frequency of 15kHz. After the residual solution in the interior and on the surface of the porous material is completely cleaned, the residual solution and salt on the surface of the active metal porous material are blown dry with high-purity argon (99.999vol.%), to obtain the biomimetic modified layer on the surface of the porous active material.

[0058] Example 4: A method for preparing a biomimetic modified layer on the surface of a porous active material, comprising the following steps:

[0059] S1. A Zn-Mg-Cu zinc alloy with a pore size of 1310μm and a porosity of 76% is prepared by SLM, and is pretreated. Specifically, the outer layer is first treated with a sandblasting machine to remove the adhered powder, and then is ultrasonically treated with 10vol.% hydrochloric acid ethanol solution for 15min. After being taken out, the Zn-Mg-Cu zinc alloy is immersed in ethanol solution and is ultrasonically vibrated again for 15min at a vibration frequency of 15kHz. The above steps are repeated for 3 times. The Zn-Mg-Cu zinc alloy is blown dry with high-purity argon (99.999vol.%) for standby;

[0060] S2. 2mg / mL lysozyme is mixed with 10mmol / L N-(2-acetamido)-2-aminoethanesulfonic acid (ACES) cell buffer with a pH of 7-8 to obtain a lysozyme type solution. The same component and proportion of cell buffer and 50mL dithiothreitol (DTT) reducing agent are mixed, and the pH is adjusted to 5.8 with 5mol / L NaOH strong alkaline solvent to obtain a reducing agent solution. The lysozyme type solution and the reducing agent solution are mixed in equal volume, and are ultrasonically vibrated to mix uniformly to obtain a lysozyme mineralization biomimetic solution for standby;

[0061] S3. The active metal porous material obtained in S1 is immersed in the lysozyme mineralization biomimetic solution obtained in S2, and is incubated in a thermostat at 20°C and a humidity of 55%. After 2 h, the active metal porous material is taken out and placed in a circulating pump containing the lysozyme mineralization biomimetic solution obtained in S2, and is treated at a circulation rate of 1.5 mL / min for 20 min. The treatment is repeated 4 times. The active metal porous material is immersed in anhydrous ethanol solvent, and is ultrasonically vibrated at a vibration frequency of 15 kHz. After the residual solution in the interior and on the surface of the porous material is completely cleaned, the residual solution and salt on the surface of the active metal porous material are dried by blowing high-purity argon (99.999 vol.%), and the porous active material surface biomimetic modification layer is obtained.

[0062] Comparative Example 1: A method for preparing a porous active material surface modification layer, comprising the following steps:

[0063] S1. A body-centered cubic AZ91D magnesium alloy with a pore size of 550 μm and a porosity of 60% is prepared by SLM, and is ready for use.

[0064] S2. 2 mg / mL lysozyme is mixed with 10 mmol / L 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES) cell buffer with a pH of 7-8 to obtain a lysozyme solution. The same proportion of cell buffer and 50 mL tris(2-carboxyethyl) phosphine hydrochloride (TCEP) reducing agent are mixed, and the pH is adjusted to 5.8 by 5 mol / L NaOH strong alkaline solvent to obtain a reducing agent solution. The lysozyme solution and the reducing agent solution are mixed in equal volumes, and are uniformly mixed by ultrasonic vibration to obtain a lysozyme mineralization biomimetic solution, which is ready for use.

[0065] S3. The active metal porous material obtained in S1 is immersed in the lysozyme mineralization biomimetic solution obtained in S2, and is incubated in a thermostat at 20°C and a humidity of 55%. After 2 h, the active metal porous material is taken out and placed in a circulating pump containing the lysozyme mineralization biomimetic solution obtained in S2, and is treated at a circulation rate of 1.5 mL / min for 20 min. The treatment is repeated 4 times. The active metal porous material is immersed in anhydrous ethanol solvent, and is ultrasonically vibrated at a vibration frequency of 15 kHz. After the residual solution in the interior and on the surface of the porous material is completely cleaned, the residual solution and salt on the surface of the active metal porous material are dried by blowing high-purity argon (99.999 vol.%), and the porous active material surface biomimetic modification layer is obtained.

[0066] Compared with Example 1, the main difference of the present comparative example is that the active metal porous material is not pretreated.

[0067] Preparation method of a porous active material surface modification layer, comprising the following steps:

[0068] S1. A body-centered cubic AZ91D magnesium alloy with a pore size of 3000 μm and a porosity of 86.4% was prepared by SLM, and pretreated, specifically including first sandblasting the outer layer of the powder using a sandblaster, then ultrasonic treating it with 10 vol.% hydrochloric acid ethanol solution for 15 min, then taking it out and immersing it in an ethanol solution and re-ultrasonic vibrating it for 15 min, with a vibration frequency of 15 kHz, repeating 3 times, then blowing it dry as a whole with high-purity argon gas with a purity of 99.999 vol.%;

[0069] S2. 2 mg / mL lysozyme was mixed with 10 mmol / L 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES) cell buffer with a pH of 7-8 to obtain a lysozyme type solution; the same proportion of cell buffer and 50 mL tris(2-carboxyethyl) phosphine hydrochloride (TCEP) reducing agent were mixed, and the pH was adjusted to 5.8 by 5 mol / L NaOH strong alkaline solvent to obtain a reducing agent solution; the lysozyme type solution and the reducing agent solution were mixed in equal volumes and ultrasonic vibration was used to mix them uniformly to obtain a lysozyme mineralization biomimetic solution, which was ready for use;

[0070] S3. The active metal porous material was thoroughly cleaned inside and on the surface with high-purity anhydrous ethanol, and the active metal porous material obtained in S1 was immersed in the lysozyme mineralization biomimetic solution obtained in S2, incubated in a thermostat at a temperature of 20°C and a humidity of 55%, incubated for 2 h, then taken out and placed in a circulating pump containing the lysozyme mineralization biomimetic solution obtained in S2, and treated with a circulation rate of 1.5 mL / min for 20 min, repeated 4 times, and then immersed in anhydrous ethanol solvent, with a vibration frequency of 15 kHz for ultrasonic vibration, and after the residual solution inside and on the surface of the porous material was completely cleaned, the residual solution and salt on the surface of the active metal porous material were blown dry with high-purity argon gas (99.999 vol.%), and the porous active material surface modification layer was obtained.

[0071] Compared with Example 1, the main difference of the present comparative example is that the pore size and porosity of the active metal porous material are too large.

[0072] Preparation method of a porous active material surface modification layer, comprising the following steps:

[0073] S1. A regular octahedron WE43 magnesium alloy with a pore size of 150 μm and a porosity of 34.5% was prepared by SLM, and pretreated, specifically including sandblasting the outer layer of the powder with a sandblasting machine, then ultrasonic treatment with 10 vol.% perchloric acid ethanol solution for 15 min, then taking it out and immersing it in an ethanol solution and then re-ultrasonic vibration for 15 min, the vibration frequency was set to 15 kHz, repeated for 3 times, then dried with high-purity argon gas (99.999 vol.%);

[0074] S2. 2 mg / mL lysozyme was mixed with 10 mmol / L N-(2-acetamido)-2-aminoethanesulfonic acid (ACES) cell buffer with a pH of 7-8 to obtain a lysozyme type solution; the same component and proportion of cell buffer and 50 mL dithiothreitol (DTT) reducing agent were mixed, and the pH was adjusted to 5.8 by 5 mol / L NaOH strong alkaline solvent to obtain a reducing agent solution; the lysozyme type solution and the reducing agent solution were taken and mixed in equal volume, and ultrasonic vibration was used to mix uniformly to obtain a lysozyme mineralization biomimetic solution, which was ready for use;

[0075] S3. The active metal porous material was washed with high-purity anhydrous ethanol to remove the internal and surface residues, and then immersed in the lysozyme mineralization biomimetic solution obtained in S2, and incubated in a thermostat at 20℃ and a humidity of 55% for 2 h, then taken out and placed in a circulating pump containing the lysozyme mineralization biomimetic solution obtained in S2, and treated with a circulation rate of 0.8 mL / min for 18 min, repeated for 3 times, then immersed in anhydrous ethanol solvent and ultrasonic vibration was performed at a vibration frequency of 15 kHz, and after the internal and surface residues of the porous material were completely removed, the surface residues and salts of the active metal porous material were dried with high-purity argon gas (99.999 vol.%), to obtain the porous active material surface modification layer.

[0076] Compared with Example 1, the main difference of the present comparative example is that the pore size and porosity of the active metal porous material are too small.

[0077] Comparative Example 4: A method for preparing a porous active material surface modification layer, comprising the following steps:

[0078] S1. A body-centered cubic pure Zn with a pore size of 550 μm and a porosity of 60% was prepared by SLM, and pretreated, specifically including: first, the outer layer of the powder was treated by sand blasting with a sand blasting machine, then the Zn was ultrasonically treated with 10 vol.% hydrochloric acid ethanol solution for 15 min, then taken out and immersed in an ethanol solution and ultrasonically vibrated for 15 min again, the vibration frequency was set to 15 kHz, the above steps were repeated for 3 times, and then the Zn was blown dry as a whole with high-purity argon with a purity of 99.999 vol.%;

[0079] S2. 2 mg / mL lysozyme was mixed with 10 mmol / L 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES) cell buffer with a pH of 7-8 to obtain a lysozyme type solution; the same component and proportion of the cell buffer was mixed with 50 mL tris(2-carboxyethyl) phosphine hydrochloride (TCEP) reducing agent, and the pH was adjusted to 5.8 by 5 mol / L NaOH strong alkaline solvent to obtain a reducing agent solution; the lysozyme type solution and the reducing agent solution were taken and mixed in equal volume, and ultrasonically vibrated to mix uniformly to obtain a lysozyme mineralization biomimetic solution, which was used.

[0080] S3. The active metal porous material was washed with high-purity anhydrous ethanol to remove the internal and surface residues, the active metal porous material obtained in S1 was immersed in the lysozyme mineralization biomimetic solution obtained in S2, and incubated in a thermostat at a temperature of 20 ℃ and a humidity of 55%, and incubated for 2 h, then the active metal porous material was immersed in anhydrous ethanol solvent and ultrasonically vibrated at a vibration frequency of 15 kHz, and after the internal and surface residues of the porous material were completely cleaned, the surface residues and salts of the active metal porous material were blown dry with high-purity argon (99.999 vol.%), to obtain the porous active material surface modification layer.

[0081] Compared with Example 3, the main difference of the present comparative example is that no circulation treatment is performed.

[0082] Comparative Example 5: A method for preparing a porous active material surface modification layer, comprising the following steps:

[0083] S1. A body-centered cubic pure Zn with a pore size of 550 μm and a porosity of 60% was prepared by SLM, and pretreated, specifically including: first, the outer layer of the powder was treated by sand blasting with a sand blasting machine, then the Zn was ultrasonically treated with 10 vol.% hydrochloric acid ethanol solution for 15 min, then taken out and immersed in an ethanol solution and ultrasonically vibrated for 15 min again, the vibration frequency was set to 15 kHz, the above steps were repeated for 3 times, and then the Zn was blown dry as a whole with high-purity argon with a purity of 99.999 vol.%;

[0084] S2. 2 mg / mL lysozyme was mixed with 10 mmol / L N-(2-acetamido)-2-aminoethanesulfonic acid (ACES) cell buffer with pH of 7-8 to obtain a lysozyme type solution; the same proportion of cell buffer and 50 mL dithiothreitol (DTT) reducing agent were mixed, and the pH was adjusted to 5.8 by 5 mol / L NaOH strong alkaline solvent to obtain a reducing agent solution; the lysozyme type solution and the reducing agent solution were mixed in equal volume, and were mixed uniformly by ultrasonic vibration to obtain a lysozyme mineralization biomimetic solution, which was ready for use;

[0085] S3. The active metal porous material obtained in S1 was immersed in the lysozyme mineralization biomimetic solution obtained in S2, and was incubated in a thermostat at a temperature of 20°C and a humidity of 55%. After 2 h, the active metal porous material was taken out and was placed in a circulating pump containing the lysozyme mineralization biomimetic solution obtained in S2, and was treated by circulation at a flow rate of 3 mL / min for 20 min, which was repeated 4 times. The active metal porous material was immersed in anhydrous ethanol solvent, and was ultrasonically vibrated at a frequency of 15 kHz. After the residual solution in the interior and on the surface of the porous material was completely cleaned, the residual solution and salt on the surface of the active metal porous material were dried by blowing high-purity argon (99.999 vol.%), and thus the surface modification layer of the porous active material was obtained.

[0086] Compared with Example 4, the main difference of the present comparative example is that the circulation treatment flow is too large.

[0087] Comparative Example 6: A method for preparing a surface modification layer of a porous active material, comprising the following steps:

[0088] S1. A body-centered cubic AZ91D magnesium alloy with a pore size of 550 μm and a porosity of 60% was prepared by SLM, and was pretreated. Specifically, the outer layer was first sandblasted to remove the adhered powder, and then was ultrasonically treated with 10 vol.% hydrochloric acid ethanol solution for 15 min. Then the active metal porous material was immersed in ethanol solution and was ultrasonically vibrated again for 15 min at a frequency of 15 kHz. The above steps were repeated 3 times, and then the active metal porous material was dried by blowing high-purity argon (99.999 vol.%), and was ready for use.

[0089] S2. 2 mg / mL lysozyme was mixed with 10 mmol / L 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES) cell buffer with pH of 7-8 to obtain a lysozyme type solution, which was ready for use;

[0090] S3. The active metal porous material obtained in S1 is immersed in the lysozyme type solution obtained in S2, and is incubated in an incubator at a temperature of 20℃ and a humidity of 55%. After 2 hours, the active metal porous material is taken out and placed in a circulating pump containing the lysozyme type solution obtained in S2, and is treated at a circulation rate of 0.8 mL / min for 18 min, repeated for 3 times. The active metal porous material is immersed in anhydrous ethanol solvent, and is ultrasonically vibrated at a vibration frequency of 15 kHz. After the residual solution in the interior and on the surface of the porous material is completely cleaned, the residual solution and salt on the surface of the active metal porous material are dried by blowing high-purity argon (99.999 vol.%), and the surface modified layer of the porous active material is obtained.

[0091] Compared with Example 1, the main difference of the present comparative example is that no reducing agent solution is added.

[0092] The parameters of each example and comparative example are shown in Table 1 below:

[0093] Table 1: Parameters of Examples 1-4 and Comparative Examples 1-6

[0094]

[0095]

[0096] The surface biomimetic modified layer of the porous active material of Example 1 is characterized and analyzed, and the results are as follows:

[0097] Figure 2 The micro cross-section morphology and element distribution map of the surface biomimetic modified layer of the porous active material of the present application is shown in the SEM and corresponding EDS map. It can be seen that the SLM active metal porous material after treatment is covered with a protective layer of hydroxyapatite with an average thickness of about 10 μm (the thinnest region is 6 μm, and the thickest region is close to 12 μm), and the thickness is relatively uniform. The key elements such as O, P, Ca, etc. in the surface biomimetic modified layer are uniformly distributed, which proves that the preparation method provided by the present application successfully prepares a protective coating on the surface and interior of the SLM active metal porous material, and the method proposed by the present application is effective and can be quickly implemented.

[0098] The test results of the remaining examples are basically consistent with them.

[0099] Figure 3The micro-morphology diagram of Example 1 of the present application. It can be seen from the diagram that the active metal porous material in Example 1 is filled with a large amount of slag powder inside, and the surface biomimetic modification layer has a small coverage area. Since the active metal porous material in Example 1 is not pretreated, on the one hand, the active metal such as Mg and Zn is extremely easy to react with the acid or alkaline solvent, which greatly consumes the effective substances in the prepared solution, resulting in that the porous component cannot be effectively modified; on the other hand, since the sticky powder in the porous component is not removed, there is still a large amount of slag powder inside, which greatly prevents the in-situ growth of the modification layer inside the active metal porous material.

[0100] Figure 4 The physical diagram of Example 2 of the present application. The pore size of the active metal porous material in Example 2 is too large, and the porosity is too high. On the one hand, it cannot effectively support the porous structure formed by SLM, and when slight corrosion occurs, it will quickly degrade and then collapse; on the other hand, the porous structure with large pore size has a significantly increased affinity with the body fluid after the surface treatment of the present application, resulting in that the liquid and the active metal porous material with high specific surface area are more likely to dissolve and fail, which greatly reduces the surface protection effect of the active metal porous material.

[0101] Figure 5 The physical diagram of Example 3 of the present application. The pore size of the active metal porous material in Example 3 is too small. Even after modification, the wettability between the surface of the active metal porous material and the body fluid is significantly improved, but due to the small pore size, it cannot promote the effective circulation of the lysozyme mineralization biomimetic solution inside, so that the surface of the active metal porous material is covered with a coating first, and then the surface pores are blocked, resulting in that the liquid flow cannot further flow into the inside of the porous structure, so that the inside is not covered with a modification layer, which greatly reduces the surface protection effect of the active metal porous material.

[0102] Figure 6 The internal OM morphology diagram of Example 4 of the present application. In Example 4, since the self-developed circulating pump is not used for sufficient treatment, although the active metal porous material surface grows an apatite modification layer in-situ during the liquid immersion process, since the inside is not covered with a modification layer, the surface coating is corroded after use, which will quickly erode the internal structure of the active metal porous material, resulting in poor protection effect.

[0103] Figure 7The physical map of the present application Comparative Example 5. The active metal porous material in Comparative Example 5 even uses a self-developed circulating pump for treatment, but due to the excessively large flow rate, the internal modification is not uniform. That is, around the active metal porous material, due to the excessively fast flow rate of the circulating pump, the surface layer is extremely easy to be repeatedly impacted by the liquid flow of the circulating pump, and even the modification layer grown in situ is extremely easy to fall off under the impact of the liquid flow, so it is difficult for the surface to be covered with the modification layer in situ; while inside the active metal porous material, due to the deceleration effect of the circulating pump liquid flow, there is more time for contact, reaction and further growth inside the porous structure, so it is easy for the modification layer to grow in situ inside the active metal porous material. However, the non-uniform growth of the modification layer greatly limits the overall protection effect of the active metal porous material.

[0104] Performance tests were performed on Examples 1-4 and Comparative Examples 1-6, and the specific test methods are shown as follows:

[0105] Mechanical property test

[0106] According to GB / T 31930-2015 / ISO 13314:2011, the SLM samples with a size of 10x10x15mm 3 before and after modification were placed in a universal compression device, the strain rate was set to 0.5mm / min for compression until fracture, and then the maximum compression strength was read.

[0107] Corrosion performance test

[0108] SLM samples with an area of 1x1 cm 2 were selected for testing, and after being inlaid with epoxy resin, they were polished. Electrochemical tests were performed in a 3.5 wt.% NaCl solution using a standard three-electrode electrochemical workstation (CS350, Wuhan, China). Pt was used as the counter electrode (CE), a saturated calomel electrode (SCE) was used as the reference electrode (RE), and the test piece was used as the working electrode. Open circuit potential (OCP) measurement lasted for 3600 s to ensure that the electrode process was in a stable state during the measurement. The frequency range for electrochemical impedance spectroscopy (EIS) measurement was set to 10 mHz - 100 kHz, and the disturbance amplitude applied was 10 mV. The polarization curve was tested within the range of OCP±500 mV, and the scan rate was 1 mV / s. The polarization resistance (Rp) was determined according to the following formula using the electrochemical parameters (icorr, β a and β c ):

[0109]

[0110] where i corr represents the corrosion rate (mm / y), β aSlope representing the anodic branch, β c Slope representing the cathodic branch. Data were analyzed using Zview3.3 software, all experimental measurements were repeated three times to ensure reproducibility.

[0111] Biological performance tests

[0112] In vitro cytotoxicity, proliferation and differentiation effects on samples were analyzed using MC3T3-E1 osteoblastic precursor cells, in accordance with international standard ISO 10993-5. Liquid extracts of the samples (3 cm 2 / ml in a-MEM with 10% FBS (v / v) at 37°C) were prepared and filter-sterilized prior to use in cytotoxicity tests, which were evaluated using a Cell Counting Kit-8 (CCK-8). BMSCs were seeded at a density of 1 x 10 4 cells per well in 96-well plates (Nest, USA) for one day, and then the culture medium was replaced with liquid extracts of medical grade polyethylene (negative control, no cytotoxicity), a-MEM with 10% FBS (v / v) and 10% dimethyl sulfoxide (DMSO) (positive control, providing a reproducible cytotoxic response), and liquid extracts from samples from each group (100 μΐ / ΐοηεΙ) for 1 day, 3 days, 5 days, and 7 days. Subsequently, 10 μΐ of CCK-8 solution was added to each well of the plate, and the plate was incubated under light for two hours. The absorbance at 450 nm was measured. The values for the negative control wells were averaged and taken as 100% cell survival. All other values were then averaged relative to their group and compared to the negative control group.

[0113] The samples were subjected to anti-Staphylococcus aureus detection, and the test method was as follows:

[0114] LB liquid medium - 100 mL of distilled water was measured into a 250 mL reagent bottle with a measuring cylinder, 2.5 g of LB broth medium was weighed with an analytical electronic balance, and after mixing, it was sterilized in a high-temperature high-pressure steam sterilization pot at 121°C for 15 min, and then used.

[0115] LB solid medium - 100 mL of distilled water was measured into a 250 mL reagent bottle with a measuring cylinder, 2.5 g of LB broth medium and 1.5 g of agar powder were weighed with an analytical electronic balance, and after mixing, it was sterilized in a high-temperature high-pressure steam sterilization pot at 121°C for 15 min. When the medium cooled to about 40-50°C, 15 mL of medium was sucked into a disposable sterile flat dish with an electric pipette.

[0116] Take 2 12 mL bacterial culture tubes, each add 3 mL of LB liquid medium, pick a single colony from the Staphylococcus aureus solid culture medium and add it to the liquid medium, the other one is blank control. Put it in a constant temperature shaker (37℃, 200rpm) and shake overnight (15h).

[0117] Wipe the surface of the sample with 75% alcohol cotton, dry it and put it in a disposable petri dish with the corresponding number. Irradiate both sides with ultraviolet light for 30 minutes for sterilization and standby.

[0118] Dilute the Staphylococcus aureus bacterial solution to 106 CFU / mL with LB liquid medium. Add 50 μL of the diluted bacterial solution to the surface of the sample, and the control group does not add the sample. Cover with a cover film and press gently. Put it in a constant temperature incubator at 37℃ and incubate for 18h.

[0119] After the culture is completed, rinse with 2 mL of sterile PBS and make serial 10-fold dilutions with PBS solution. Take 100 μL of the diluted solution and evenly spread it on LB solid medium. Incubate in a constant temperature incubator at 37℃ for 18h. Take it out, take a picture and record the number of colonies. Then count the colonies according to GB4789.2-2016 and calculate the antibacterial rate.

[0120] Figure 8 The cell staining diagram of Example 1 and Comparative Example 6 of the present application is shown on the left for Comparative Example 6 and on the right for Example 1. As can be seen from the diagram, after growing for 8 weeks, the cell growth on the surface of the active porous material of Comparative Example 6 is far worse than that of the porous material treated by the method.

[0121] Figure 9 The cell diagram of Example 1 and the porous active material without treatment of the present application is shown. As can be seen from the diagram, after growing for 1 day, the cell growth on the surface of the active porous material without treatment is not as good as that of the porous material treated by the method. At the same time, due to the rapid degradation of the porous material without treatment, the cells without treatment die more, which is not as good as the cell growth state on the surface of the porous material after overall modification.

[0122] The specific results are shown in the following table:

[0123] Table 2 Test results of Examples 1-4 and Comparative Examples 1, 3-5

[0124]

[0125] Among them, Comparative Example 2 cannot be formed due to rapid corrosion, so it does not perform performance test. Comparative Example 6 does not add reducing agent and directly uses lysozyme solvent, which cannot promote the growth of hydroxyapatite film layer on the surface of the active material, so it does not perform performance test.

[0126] As can be seen from the above table, the surface biomimetic modification layer of the porous active material prepared by each embodiment of the present application has excellent compressive strength and corrosion resistance, the antibacterial rate is about 99%, and the cell survival rate is higher than 90%, which shows excellent antibacterial property, bone integration promotion property and good mechanical strength, can realize controllable degradation of the porous alloy material, and is suitable for bone implant.

[0127] The active metal porous material of Comparative Example 1 is not pretreated, is filled with a large amount of slag powder inside, has a small surface biomimetic modification layer coverage area, has a high self-corrosion current density, has poor corrosion resistance, has low antibacterial rate and cell survival rate, and has poor bioactivity; the active metal porous material of Comparative Example 3 has too small pore size and porosity, the surface biomimetic modification layer cannot grow fully, has poor corrosion resistance, the antibacterial rate is less than 90%, and the cell survival rate is less than 90%; Comparative Example 4 is not subjected to cyclic treatment, the inside is not full of modification layers, the surface coating is corroded away during use, will quickly erode the internal structure of the active metal porous material, and results in poor protection effect and low cell survival rate; and the cyclic treatment flow of Comparative Example 5 is too large, the modification layer grows unevenly, greatly affects the overall protection effect, and the cell survival rate is only about 80%.

[0128] In summary, the hydroxyapatite biomimetic coating formed in situ on the porous active material of the present application cleverly imitates the mineralized bone tissue outside the peripheral bone tissue, and is very suitable for the adhesion of osteoblasts on the surface thereof; and the porous active metal scaffold formed by the SLM technology forms a plurality of micro-nano holes after surface modification, promotes the further climbing of osteoblasts, and further improves the bone integration property thereof. In combination with the Mg 2+ , Zn 2+ , Cu 1+ / Cu 2+ plasma products formed after degradation of the active metal, the excellent antibacterial property is exhibited, the preparation method is simple and fast, is suitable for a variety of active degradable metal materials, the in-situ formed hydroxyapatite coating is not only closely combined with the substrate, but also can obtain a uniform surface biomimetic modification layer on the inner and outer surfaces of different types of active metal porous materials, not only improves the strength and hardness thereof, but also improves the corrosion resistance thereof, and promotes the degradation rate thereof in the actual service process to be greatly reduced.

[0129] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, and are not intended to limit the protection scope of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced by equivalents without departing from the spirit and scope of the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A method for preparing a biomimetic modification layer on a porous active material surface, characterized in that The method comprises the following steps: S1. Preparing an active metal porous material with a pore size of 400-2000 μm and a porosity of 40-80% by SLM, and performing pretreatment on the active metal porous material, wherein the pretreatment comprises surface sand blasting, ultrasonic cleaning, repeating the ultrasonic cleaning step 3-5 times, drying, and standing by; S2. Mixing lysozyme with a cell buffer to obtain a lysozyme type solution; mixing the cell buffer with a reducing agent in the same proportion to obtain a reducing agent solution by adjusting the pH to 5-6.8; and mixing the lysozyme type solution and the reducing agent solution in equal volumes to obtain a lysozyme mineralization biomimetic solution, which is ready for use; S3. Immersing the active metal porous material obtained in S1 in the lysozyme mineralization biomimetic solution obtained in S2, incubating, taking out, and placing in a circulating pump containing the lysozyme mineralization biomimetic solution obtained in S2, and performing 0.5-2 mL / min circulation treatment for 15-20 min, repeating 3-5 times, cleaning, and drying to obtain the biomimetic modified layer on the surface of the porous active material; The active metal porous material in S1 is one or more of a magnesium alloy, pure Zn, and a zinc alloy, and the porous structure is body-centered cubic and / or regular octahedral; The cleaning medium in the ultrasonic cleaning in S1 is one or more of 5-20 vol.% perchloric acid alcohol, 3-5 vol.% nitric acid alcohol, and 10-20 vol.% dilute hydrochloric acid, the vibration frequency is 10-20 kHz, and the ultrasonic time is 10-20 min; The reducing agent in S2 is one or more of tris(2-carboxyethyl)phosphine hydrochloride, dithiothreitol, and tris(3-hydroxypropyl)phosphine; The incubation in S3 is incubation in a thermostat, the temperature is 18-37 °C, the relative humidity is 45-60%, and the incubation time is 1.5-3 h.

2. A method for preparing the biomimetically modified layer of a porous active material surface according to claim 1, characterized in that, The drying in S1 is blowing dry with a high-pressure jet of an inert gas, and the inert gas is 99.999 vol.% high-purity argon and / or nitrogen.

3. A method for preparing the biomimetic modified layer of the porous active material surface according to claim 1, characterized by, The cell buffer in S2 comprises one or more of 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid, N-(2-acetamido)-2-aminoethanesulfonic acid, and 3-(N-morpholino)propanesulfonic acid; and the pH of the cell buffer is 7-8.

4. A method for preparing the biomimetically modified layer of a porous active material surface according to claim 1, characterized by, The adjustment of the pH to 5-6.8 in S2 is adjustment by a strong alkaline solvent; and the strong alkaline solvent is one or more of NaOH, KOH, and Ca(OH)2.

5. A method for preparing the biomimetically modified layer of a porous active material surface according to claim 1, characterized by, The cleaning in S3 is cleaning of the inside and surface of the porous material with a high-purity organic solvent; the high-purity organic solvent is one or more of anhydrous ethanol, dimethyl carbonate, and diethyl carbonate; and the drying in S3 is blowing off the residual solution and salt on the surface of the active metal porous material with an inert gas; and the inert gas is 99.999 vol.% high-purity argon and / or nitrogen.

6. A porous active material surface biomimetic modification layer, characterized in that, The biomimetic modified layer on the surface of the porous active material is prepared by the method in any one of claims 1-5.

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