CN111701571B - Adsorbent for removing urea, preparation method and application thereof, and adsorption device - Google Patents
Adsorbent for removing urea, preparation method and application thereof, and adsorption device Download PDFInfo
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Abstract
The invention provides an adsorbent for removing urea, and a preparation method, application and an adsorption device thereof, and relates to the technical field of biological medicines. The adsorbent is prepared by the following method: and adding a carbon carrier in the process of preparing the Zn-ZIF metal organic framework material, and sequentially carrying out high-temperature carbonization and low-temperature oxidation on the obtained carbon-doped Zn-ZIF metal organic framework material to obtain the carbon-doped Zn-ZIF metal organic framework material. According to the invention, the carbon material-nano zinc oxide composite adsorbent is obtained by using a carbon material as a carrier and a metal organic framework material as a precursor, carbonizing at high temperature and oxidizing according to the bonding effect of nitrogen atoms or oxygen atoms in urea molecules between zinc atoms on the surface of ZnO. The adsorbent is simple to prepare, has high adsorption capacity, high selectivity, good biological and blood compatibility and relatively low cost, has the adsorption effect not influenced by the pH value of the peritoneal dialysis solution, and provides a new treatment method for removing excessive urea in the peritoneal dialysis solution of a patient.
Description
Technical Field
The invention relates to the technical field of biological medicines, in particular to an adsorbent for removing urea, and a preparation method, application and an adsorption device thereof.
Background
The kidney plays an extremely important role in human metabolism. Once renal function is reduced or lost, various endogenous chemical components such as urea, creatinine, uric acid and middle molecular substances are accumulated in blood, and various diseases are caused. Renal failure is a pathological condition in which kidney function is partially or completely lost as a result of various kidney diseases progressing to a later stage. In the end stage of chronic renal failure, the collection of symptoms is also known as uremia, and the reserve and filter function of the kidneys is essentially lost. Peritoneal dialysis is an important mode of maintenance therapy for patients with end-stage renal disease. Currently, in clinical practice, urea clearance index (Kt/V) is a key indicator to assess whether peritoneal dialysis is adequate. Therefore, it is urgent to develop a urea adsorbent having good adsorption performance in the peritoneal dialysis solution of pH = 5.2.
At the present stage, the adsorbent for removing urea mainly comprises amino-functionalized adsorbent (amino-SiO) 2 ) Modified chitosan, aldehyde-based functional adsorbents (oxidized cellulose, oxidized starch, cross-linked oxidized cyclodextrin and the like), urease, polymer-coated activated carbon and the like. The urea enzymolysis is the method for adsorbing urea which is commonly adopted at present, the problem of removing carbon dioxide and ammonium ions which are enzymolysis products needs to be solved, the removal of the carbon dioxide needs to be realized by degassing, and NH 4 + Zirconium phosphate is commonly used for scavenging. However, on the one hand, urease is not well preserved per se, and on the other hand, zirconium phosphate cation resin is used for adsorbing NH 4 + Then, hydrogen ions or sodium ions are introduced to change the pH of the dialysate, and the pH of the peritoneal dialysis solution needs to be further adjusted by supplementing electrolytes. Furthermore, adsorption of urea by the aldehyde-group functionalized adsorbent is mainly performed under neutral conditions through Schiff base reaction between the aldehyde group of the aldehyde-group functionalized adsorbent and urea, while pH =5.2 of peritoneal fluid affects the Schiff base reaction due to improper pH, and high or low pH may cause decomposition of Schiff base condensation products, thereby reducing the adsorption amount.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The object of the present invention is to provide an adsorbent for urea removal, a method for its preparation, use, an adsorption device, to alleviate at least one of the above technical problems.
In order to realize the purpose, the following technical scheme is adopted:
in a first aspect, the present invention provides an adsorbent for urea removal, prepared by the following method:
and adding a carbon carrier in the process of preparing the Zn-ZIF metal organic framework material, and sequentially carrying out high-temperature carbonization and low-temperature oxidation on the obtained carbon-doped Zn-ZIF metal organic framework material to obtain the adsorbent.
In a second aspect, the present invention provides a method for preparing the above adsorbent for removing urea, comprising the following steps:
(a) Dispersing a carbon carrier in an alcohol solvent;
(b) Dissolving a zinc source in (a);
(c) Pouring the organic ligand precursor solution into the (b) and mixing;
(d) Standing the solution obtained in the step (c) at room temperature overnight, or putting the solution into a hydrothermal reaction kettle for overnight heating, separating, washing and drying;
(e) After drying is finished, carrying out high-temperature carbonization under the condition of protective gas;
(f) After carbonization is finished, low-temperature oxidation is carried out;
(g) And (4) drying in vacuum to obtain the adsorbent.
In a third aspect, the invention provides an application of the adsorbent for removing urea in preparation of a peritoneal dialysis biomedical material.
In a fourth aspect, the present invention provides an adsorption plant comprising the above adsorbent for urea removal.
The invention has the following beneficial effects:
(1) According to the invention, the carbon material is introduced as a carrier in the process of preparing the Zn-ZIF MOFs material, the carbon-doped Zn-ZIF MOFs material is obtained, and the Zn-ZIF MOFs material is attached to micropores of the carbon material, so that the problems that the ZIF is a nano particle and is easy to agglomerate and not easy to disperse are solved, and the Zn-ZIF MOFs material and the carbon material can generate a synergistic effect, so that the adsorption performance is more excellent.
(2) According to ZnO generated by oxidizing the Zn-ZIF MOFs material after high-temperature carbonization, surface zinc atoms of the ZnO can generate bonding action with nitrogen atoms or oxygen atoms in urea molecules, so that urea is selectively adsorbed by chemical action, urea is physically adsorbed by utilizing the high specific surface areas of the Zn-ZIF MOFs material and the carbon material through hydrophobic action, and high adsorption capacity can be obtained by double adsorption.
(3) The adsorbent is simple to prepare, has high adsorption capacity, high selectivity, good biological and blood compatibility and relatively low cost, the adsorption effect is not influenced by the pH value of the peritoneal dialysis solution, the adsorbent can be used in peritoneal dialysis, a new treatment method is provided for removing excessive urea in the peritoneal dialysis solution of a patient, and the saturated adsorption capacity of the adsorbent to the urea can reach 136.8mg/g.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a graph showing the results of a static adsorption test of the adsorbent of the present invention on urea adsorbed in peritoneal fluid;
FIG. 2 is a graph showing the results of the cytotoxicity evaluation test of the adsorbent of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
According to a first aspect of the present invention, there is provided an adsorbent for urea removal, prepared by the following method: and adding a carbon carrier in the process of preparing the Zn-ZIF metal organic framework material, and sequentially carrying out high-temperature carbonization and low-temperature oxidation on the obtained carbon-doped Zn-ZIF metal organic framework material to obtain the adsorbent.
[ Zn-ZIF-based organometallic framework Material ]
ZIFs (zeolite imidazole-like framework materials) are metal organic framework Materials (MOFs) with a zeolite framework structure, which are generated by reacting Zn or Co as a metal source and imidazole or an imidazole derivative as an organic ligand in a solvent.
The Zn-ZIF metal organic framework material is a metal organic framework material with a zeolite framework structure, which is generated by the reaction of Zn serving as a metal source and imidazole or an imidazole derivative serving as an organic ligand in a solvent.
Typical, but non-limiting examples of ZIFs are ZIF-8 (Zn [ MelM ]] 2 (MelM＝ 2 -methylimidazole)), ZIF-1, ZIF-10, ZIF-64 ([ Zn (IM) ] 2 ](IM = imidazole)), ZIF-5[ Zn ], [ 4 O(bdc) 3 Bdc = terephthalic acid]，ZIF-74[Zn 2 DO(bdc)，H 4 DOBDC =2, 5-dihydroxyterephthalic acid]Namely, the Zn-ZIF metal-organic framework material is not limited to ZIF-8, but also comprises a class of ZIF metal-organic framework materials taking metal zinc ions and ion clusters thereof as nodes.
[ carbon-based Carrier ]
Carbon-based supports include, but are not limited to, activated carbon, graphene, carbon nanotubes, and the like.
And adding a carbon carrier to obtain the carbon-doped Zn-ZIF MOFs material, wherein the Zn-ZIF MOFs material is attached to micropores of the carbon material.
[ high temperature carbonization ] and [ Low temperature Oxidation ]
The high and low temperatures in the high temperature carbonization and the low temperature oxidation are a relative concept. The high temperature is generally above 600 ℃ and the low temperature is generally below 400 ℃.
The high-temperature carbonization is carried out under the condition of protective gas, and the low-temperature oxidation is carried out under the condition of oxygen.
The purpose of carbonization is to burn off organic matters in the MOF to obtain metal zinc, and the metal zinc reacts with the organic matters after oxidation to obtain a final product ZnO.
The metal organic framework Materials (MOFs) are in a highly regular network framework structure formed by self-assembly through coordination by taking metal cations or metal ion clusters as nodes and organic ligands as connecting points. Due to the excellent structural stability, a good structural framework can still be maintained after high-temperature calcination, and the unique physicochemical characteristics of large specific surface area, porosity and the like of the composite material are kept, so that the composite material is a good choice for being used as a template or a precursor. However, the metal organic framework material is a nano particle, which is not only easy to agglomerate but also not easy to disperse, and if the metal organic framework material is directly and independently applied to peritoneal dialysis to remove urea, the metal organic framework material inevitably leaks into the body of a patient to cause thrombus and further block blood vessels. The Zn-ZIF MOFs material and the carbon material are doped to prepare the composite material, so that the MOFs leakage problem can be effectively avoided, the original properties and functions of the MOFs can be kept, the porosity, specific surface area and form of the MOFs can be improved, new specific functional characteristics are provided, and the synergistic effect between the MOFs material and the functional material can endow the composite material with more excellent performance.
According to ZnO generated by oxidizing Zn-ZIF MOFs materials after high-temperature carbonization, the surface zinc atoms of the ZnO can be bonded with nitrogen atoms or oxygen atoms in urea molecules, a carbon material is designed to be used as a carrier, a Zn-ZIF MOFs material is designed to be used as a precursor, and the ZnO is oxidized after high-temperature carbonization, so that the carbon material-nano zinc oxide (such as ACs @ ZnO) composite adsorbent is obtained. The adsorbent can be used for removing urea in the peritoneal dialysis liquid efficiently through physical adsorption and chemical double adsorption. Not only does not introduce other ions to change the pH value of the peritoneal dialysis solution, but also the adsorption effect is not influenced by the pH value. And has good blood and biocompatibility.
In a preferred embodiment, the carbon-based support is activated carbon;
preferably, the activated carbon has a particle size of 200 to 1000 μm (e.g., 200 to 300, 200 to 400, 300 to 500, 300 to 600, 400 to 800, 500 to 900, 500 to 1000 μm) and a specific surface area of 500 to 1700m 2 (e.g., 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 100, 1600, or 1700 m) 2 Per g) pore volume of 0.95 to 4.68cm 3 In terms of/g (e.g. 0.95, 1.25, 2.15, 2.45, 3.65 or 4.56 cm) 3 /g)；
Preference is given toThe particle size of the active carbon is 400-800 mu m, and the specific surface area is 800-1500m 2 Per g, pore volume of 1.26-3.89cm 3 /g。
Activated Carbon (ACs) is a porous carbon material, has high porosity, chemical stability and large specific surface area, and also shows good performance in the aspect of adsorption. Researches find that ACs are introduced in the preparation process of Zn-ZIF MOFs materials to generate composite materials with large specific surface area, so that more microporous structures are formed, and adsorption is facilitated.
In a preferred embodiment, the mass ratio of the carbon-based carrier to the organic ligand precursor used for preparing the Zn-ZIF-based metal organic framework material is 10:1-10 (e.g. 10:3-8.
By controlling the mass ratio of the carbon carrier to the organic ligand precursor, the carbon carrier and the organic ligand precursor can be better matched to obtain better adsorption performance.
In a preferred embodiment, the high temperature carbonization is carried out under a protective gas (e.g., high purity argon, high purity nitrogen, etc.) at a temperature of 600-800 ℃ (e.g., 600, 650, 700, 750, or 800 ℃) for 2-6 hours (e.g., 2, 3, 4, 5, or 6 hours);
preferably, the high-temperature carbonization is carried out under the condition of protective gas, the temperature is 650-750 ℃, and the time is 2.5-4.5h;
further preferably, the low temperature oxidation is carried out under oxygen conditions at a temperature of 300-400 ℃ (e.g., 300, 320, 340, 350, 380 or 400 ℃) for a period of 1-3 hours (e.g., 1, 2 or 3 hours), preferably for a period of 1.5-2.5 hours.
The complete carbonization and oxidation are ensured by controlling the temperature and time of the high-temperature carbonization and the low-temperature oxidation.
According to a second aspect of the present invention, there is provided a method for preparing the above adsorbent for urea removal, comprising the steps of:
(a) Dispersing a carbon-based carrier in an alcohol solvent;
(b) Dissolving a zinc source in (a);
(c) Pouring the organic ligand precursor solution into the (b) and mixing;
(d) Standing the solution obtained in the step (c) at room temperature overnight, or putting the solution into a hydrothermal reaction kettle, heating the solution overnight, separating, washing and drying the solution;
(e) After drying is finished, carrying out high-temperature carbonization under the condition of protective gas;
(f) After carbonization is finished, low-temperature oxidation is carried out;
(g) And (4) drying in vacuum to obtain the adsorbent.
The adsorbent of the invention has the advantages of simple preparation, high adsorption capacity, high selectivity, good biological and blood compatibility and relatively low cost.
The descriptions of the carbon-based carrier, the high-temperature carbonization, and the low-temperature oxidation in the second aspect are the same as those in the first aspect, and are not repeated here.
In step (a), the alcoholic solvent includes, but is not limited to, ethanol, methanol, propanol, and the like.
In step (b), the zinc source includes, but is not limited to, zinc nitrate (Zn (NO) 3 ) 2 ·6H 2 O), zinc chloride, and the like.
In step (c), the organic ligand precursor includes, but is not limited to, 2-methylimidazole, imidazole, and the like.
In a preferred embodiment, the mass ratio of the carbon-based carrier to the organic ligand precursor is 10:1-10, preferably 10:3-8;
in a preferred embodiment, the concentration of the carbon-based carrier is 10 to 20mg/mL;
in a preferred embodiment, the molar ratio of zinc source to the organic ligand precursor is 1:4.2.
in a preferred embodiment, the carbon-based support is activated carbon;
preferably, the activated carbon has a particle size of 200 to 1000 μm (e.g., 200 to 300, 200 to 400, 300 to 500, 300 to 600, 400 to 800, 500 to 900, 500 to 1000 μm) and a specific surface area of 500 to 1700m 2 (e.g., 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 100, 1600, or 1700 m) 2 Per g) pore volume of 0.95 to 4.68cm 3 In terms of/g (e.g. 0.95, 1.25, 2.15, 2.45, 3.65 or 4.56 cm) 3 /g)；
Preferably, the particle size of the activated carbon is 400-800 mu m, and the specific surface area is 800-1500m 2 Per g, pore volume of 1.26-3.89cm 3 /g。
In a preferred embodiment, the high temperature carbonization in step (e) is carried out at a temperature of 600-800 ℃ for a time of 2-6h;
preferably, the high-temperature carbonization temperature is 650-750 ℃, and the time is 2.5-4.5h;
further preferably, the temperature of the low-temperature oxidation in the step (f) is 300-400 ℃, and the time is 1-3 hours, preferably 1.5-2.5 hours;
further preferably, the temperature of vacuum drying in the step (g) is 60-100 ℃ and the time is 6-12h;
preferably, the temperature of the vacuum drying is 80-100 ℃, and the time is 8-10h.
As a preferred embodiment, a preparation method of a typical adsorbent for removing urea in peritoneal dialysis solution comprises the following specific steps:
(1) Dispersing a certain amount of activated carbon in methanol;
(2) Zn (NO) is added by stirring 3 ) 2 ·6H 2 Dissolving O in (1);
(3) Quickly pouring the 2-methylimidazole solution into the step (2), and violently stirring;
(4) Placing the solution obtained in the step (3) at room temperature overnight, centrifuging, thoroughly washing, and drying in a vacuum furnace;
(5) After drying, placing the mixture in a tubular furnace, and carbonizing the mixture at high temperature under the argon condition;
(6) After carbonization, oxidizing at low temperature;
(7) Vacuum drying to obtain the ACs @ ZnO composite adsorbent.
Wherein the concentration of the active carbon is 10-20mg/mL, zn (NO) 3 ) 2 ·6H 2 The molar ratio of O to 2-methylimidazole is 1:4.2.
according to a third aspect of the present invention, there is provided a use of the above adsorbent for urea removal for the preparation of a biomedical material for peritoneal dialysis.
The adsorbent of the invention provides a new treatment method for removing excessive urea in the peritoneal dialysis fluid of a patient, the saturated adsorption capacity can reach 136.8mg/g, and the application prospect is wide.
According to a fourth aspect of the present invention, there is provided an adsorption apparatus comprising the above adsorbent for urea removal.
The adsorption device includes, but is not limited to, blood perfusion, hemofiltration, peritoneal dialysis, etc.
The adsorption apparatus has the same advantages as the adsorbent of the present invention and will not be described herein.
For further understanding of the present invention, the method and effects of the present invention will be described in further detail below with reference to specific examples and comparative examples. The following examples are merely illustrative of the present invention and should not be construed as limiting the scope of the invention. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
Wherein "@" means "and"; "ACs" represents "activated carbon" and "MOFs-ZIF" represents "Zn-ZIF metal-organic framework material".
Example 1
(1) Preparing ACs @ MOFs-ZIF-8:
weighing 10.5268g of activated carbon (particle size of 400-600 μm, specific surface area of 1384 m) 2 (iv) g; pore volume is 3.72cm 3 /g) dissolved in 100mL of methanol solution by ultrasonic dispersion, and after the dispersion is completed, 4.9673g of Zn (NO) is added under stirring 3 ) 2 ·6H 2 O, after dissolving, quickly adding 6.7415g of 2-methylimidazole, and violently stirring for 15 min; standing at room temperature overnight, centrifuging for 1, washing thoroughly, and drying in vacuum drying oven at 60 deg.C for 12h to obtain ACs @ MOFs-ZIF-8.
(2) Preparation of ACs @ ZnO:
adding the ACs @ MOFs-ZIF-8 5g (dry weight) prepared in the step (1) into a crucible, placing the crucible in a tube furnace, introducing argon for 30min, continuously introducing argon after air is completely removed, heating at the speed of 5 ℃/min, keeping at 750 ℃ for 2.5h to completely carbonize the MOFs, continuously introducing argon, cooling at the speed of 10 ℃/min, stopping introducing argon and starting introducing oxygen after the temperature is reduced to 320 ℃, keeping at the condition for 2.5h to completely oxidize the metal zinc, stopping introducing oxygen, cooling to room temperature at the speed of 20 ℃/min, drying in a vacuum drying box at 80 ℃ for 10h, wherein the serial number is) ACs @ ZnO-1.
Example 2
(1) Preparing ACs @ MOFs-ZIF-8:
10.1897g of activated carbon (particle size 400-600 μm, specific surface area 1384 m) 2 (ii)/g; pore volume is 3.72cm 3 /g) dissolved in 100mL of methanol solution by ultrasonic dispersion, and after complete dispersion, 7.8269g of Zn (NO) is added under stirring 3 ) 2 ·6H 2 O, after dissolving, quickly adding 10.6225g of 2-methylimidazole, and violently stirring for 15 min; standing at room temperature overnight, centrifuging, washing thoroughly, and drying in vacuum drying oven at 60 deg.C for 12h to obtain ACs @ MOFs-ZIF-8.
(2) Preparation of ACs @ ZnO:
adding the ACs @ MOFs-ZIF-8 g (dry weight) prepared in the step (1) into a crucible, placing the crucible in a tube furnace, introducing argon for 30min, continuing to introduce the argon after completely removing air, raising the temperature at the speed of 5 ℃/min, keeping the temperature at 650 ℃ for 4.5h to completely carbonize the MOFs, continuing to introduce the argon, reducing the temperature at the speed of 10 ℃/min, stopping introducing the argon and starting to introduce oxygen after reducing the temperature to 400 ℃, keeping the temperature for 1.5h under the condition to completely oxidize the metal zinc, stopping introducing the oxygen, reducing the temperature to room temperature at the speed of 20 ℃/min, and drying the metal zinc in a vacuum drying box at 80 ℃ for 10h with the number of) ACs @ ZnO-2.
Example 3
(1) Preparing ACs @ MOFs-ZIF-8:
weighing 10.0579g of activated carbon (granularity is 400-600 μm, specific surface area is 1384 m) 2 (iv) g; pore volume is 3.72cm 3 /g) dissolved in 100mL of methanol solution by ultrasonic dispersion, and after complete dispersion, 10.4574g of Zn was added with stirring(NO 3 ) 2 ·6H 2 O, after dissolving, quickly adding 14.1926g of 2-methylimidazole, and violently stirring for 15 min; standing at room temperature overnight, centrifuging, washing thoroughly, and drying in vacuum drying oven at 60 deg.C for 12h to obtain ACs @ MOFs-ZIF-8.
(2) Preparation of ACs @ ZnO:
adding the ACs @ MOFs-ZIF-8 5g (dry weight) prepared in the step (1) into a crucible, placing the crucible in a tube furnace, introducing argon for 30min, continuously introducing argon after air is completely removed, heating at the speed of 5 ℃/min, keeping the temperature at 700 ℃ for 3.5h to completely carbonize the MOFs, continuously introducing argon, cooling at the speed of 10 ℃/min, stopping introducing argon and starting introducing oxygen after the temperature is reduced to 360 ℃, keeping the temperature for 2h under the condition to completely oxidize the metal zinc, stopping introducing oxygen, cooling to room temperature at the speed of 20 ℃/min, drying in a vacuum drying box at the temperature of 80 ℃ for 10h, and numbering as) ACs @ ZnO-3.
Example 4
(1) Preparing ACs @ MOFs-ZIF-8:
weighing 10.5268g of activated carbon (the particle size is between 600 and 800 mu m, and the specific surface area is 1497 m) 2 (iv) g; pore volume of 3.85cm 3 /g) dissolved in 100mL of methanol solution by ultrasonic dispersion, and after complete dispersion, 4.9673g of Zn (NO) is added under stirring 3 ) 2 ·6H 2 O, after dissolving, rapidly adding 6.7415g of 2-methylimidazole, and violently stirring for 15 min; standing at room temperature overnight, centrifuging, washing thoroughly, and drying in vacuum drying oven at 60 deg.C for 12h to obtain ACs @ MOFs-ZIF-8.
(2) Preparation of ACs @ ZnO:
adding the ACs @ MOFs-ZIF-8 g (dry weight) prepared in the step (1) into a crucible, placing the crucible in a tube furnace, introducing argon for 30min, continuing to introduce the argon after completely removing air, raising the temperature at the rate of 5 ℃/min, keeping the temperature at 680 ℃ for 3h to completely carbonize the MOFs, continuing to introduce the argon, reducing the temperature at the rate of 10 ℃/min, stopping introducing the argon and starting to introduce oxygen after reducing the temperature to 320 ℃, keeping the temperature for 1.5h under the condition to completely oxidize the metal zinc, stopping introducing the oxygen, reducing the temperature to room temperature at the rate of 20 ℃/min, drying the metal zinc in a vacuum drying oven at 90 ℃ for 9h, wherein the number is ACs @ ZnO-4.
Example 5
(1) Preparing ACs @ MOFs-ZIF-8:
weighing 10.1897g of activated carbon (the particle size is between 600 and 800 mu m, and the specific surface area is 1497m 2 (ii)/g; pore volume is 3.85cm 3 /g) dissolved in 100mL of methanol solution by ultrasonic dispersion, and after complete dispersion, 7.8269g of Zn (NO) is added under stirring 3 ) 2 ·6H 2 O, after dissolving, rapidly adding 10.6225g of 2-methylimidazole, and violently stirring for 15 min; standing at room temperature overnight, centrifuging, washing thoroughly, and drying in vacuum drying oven at 60 deg.C for 12h to obtain ACs @ MOFs-ZIF-8.
(2) Preparation of ACs @ ZnO:
adding the ACs @ MOFs-ZIF-8 g (dry weight) prepared in the step (1) into a crucible, placing the crucible in a tube furnace, introducing argon for 30min, continuing to introduce the argon after completely removing air, raising the temperature at the rate of 5 ℃/min, keeping the temperature at 680 ℃ for 3h to completely carbonize the MOFs, continuing to introduce the argon, reducing the temperature at the rate of 10 ℃/min, stopping introducing the argon and starting to introduce oxygen after reducing the temperature to 320 ℃, keeping the temperature for 1.5h under the condition to completely oxidize the metal zinc, stopping introducing the oxygen, reducing the temperature to room temperature at the rate of 20 ℃/min, drying the metal zinc in a vacuum drying oven at 90 ℃ for 9h, wherein the reference is ACs @ ZnO-5.
Example 6
(1) Preparing ACs @ MOFs-ZIF-8:
weighing 10.0579g of activated carbon (the particle size is between 600 and 800 mu m, and the specific surface area is 1497m 2 (iv) g; pore volume is 3.85cm 3 /g) dissolved in 100mL of methanol solution by ultrasonic dispersion, and 10.4574g of Zn (NO) was added with stirring after complete dispersion 3 ) 2 ·6H 2 O, after dissolving, rapidly adding 14.1926g of 2-methylimidazole, and violently stirring for 15 min; standing at room temperature overnight, centrifuging, washing thoroughly, and drying in vacuum drying oven at 60 deg.C for 12h to obtain ACs @ MOFs-ZIF-8.
(2) Preparation of ACs @ ZnO:
adding the ACs @ MOFs-ZIF-8 g (dry weight) prepared in the step (1) into a crucible, placing the crucible in a tube furnace, introducing argon for 30min, continuing to introduce the argon after completely removing air, raising the temperature at the rate of 5 ℃/min, keeping the temperature at 680 ℃ for 3h to completely carbonize the MOFs, continuing to introduce the argon, reducing the temperature at the rate of 10 ℃/min, stopping introducing the argon and starting to introduce oxygen after reducing the temperature to 320 ℃, keeping the temperature for 1.5h under the condition to completely oxidize the metal zinc, stopping introducing the oxygen, reducing the temperature to room temperature at the rate of 20 ℃/min, drying the metal zinc in a vacuum drying oven at 90 ℃ for 9h, wherein the number is) ACs @ ZnO-6.
Example 7
(1) Preparing ACs @ MOFs-ZIF-8:
10.5268g of activated carbon (particle size of 400-800 μm, specific surface area of 1154 m) is weighed 2 (ii)/g; pore volume of 2.61cm 3 /g) dissolved in 100mL of methanol solution by ultrasonic dispersion, and after complete dispersion, 4.9673g of Zn (NO) is added under stirring 3 ) 2 ·6H 2 O, after dissolving, rapidly adding 6.7415g of 2-methylimidazole, and violently stirring for 15 min; standing at room temperature overnight, centrifuging, washing thoroughly, and drying in vacuum drying oven at 60 deg.C for 12h to obtain ACs @ MOFs-ZIF-8.
(2) Preparation of ACs @ ZnO:
adding the ACs @ MOFs-ZIF-8 g (dry weight) prepared in the step (1) into a crucible, placing the crucible in a tube furnace, introducing argon for 30min, continuing to introduce the argon after completely removing air, raising the temperature at the speed of 5 ℃/min, keeping the temperature at 680 ℃ for 3h to completely carbonize the MOFs, continuing to introduce the argon, reducing the temperature at the speed of 10 ℃/min, stopping introducing the argon and starting to introduce oxygen after reducing the temperature to 320 ℃, keeping the temperature for 1.5h under the condition to completely oxidize the metal zinc, stopping introducing the oxygen, reducing the temperature to room temperature at the speed of 20 ℃/min, drying the metal zinc in a vacuum drying oven at 100 ℃ for 8h, wherein the number is) ACs @ ZnO-7.
Example 8
(1) Preparing ACs @ MOFs-ZIF-8:
10.5268g of activated carbon (particle size of 400-800 μm, specific surface area of 1154 m) is weighed 2 (ii)/g; pore volume of 2.61cm 3 /g) ultrasonic dispersion dissolved in 100mL of methanol solutionAfter complete dispersion, 4.9673g of Zn (NO) were added with stirring 3 ) 2 ·6H 2 O, after dissolving, rapidly adding 6.7415g of 2-methylimidazole, and violently stirring for 15 min; standing at room temperature overnight, centrifuging, washing thoroughly, and drying in vacuum drying oven at 60 deg.C for 12h to obtain ACs @ MOFs-ZIF-8.
(2) Preparation of ACs @ ZnO:
adding the ACs @ MOFs-ZIF-8 g (dry weight) prepared in the step (1) into a crucible, placing the crucible in a tube furnace, introducing argon for 30min, continuing to introduce the argon after completely removing air, raising the temperature at the speed of 5 ℃/min, keeping the temperature at 680 ℃ for 3h to completely carbonize the MOFs, continuing to introduce the argon, reducing the temperature at the speed of 10 ℃/min, stopping introducing the argon and starting to introduce oxygen after reducing the temperature to 320 ℃, keeping the temperature for 1.5h under the condition to completely oxidize the metal zinc, stopping introducing the oxygen, reducing the temperature to room temperature at the speed of 20 ℃/min, drying the metal zinc in a vacuum drying oven at 100 ℃ for 8h, wherein the number is) ACs @ ZnO-8.
Example 9
(1) Preparing ACs @ MOFs-ZIF-8:
weighing 10.5268g of activated carbon (the particle size is between 400 and 800 mu m, and the specific surface area is 1154 m) 2 (iv) g; pore volume of 2.61cm 3 /g) dissolved in 100mL of methanol solution by ultrasonic dispersion, and after the dispersion is completed, 4.9673g of Zn (NO) is added under stirring 3 ) 2 ·6H 2 O, after dissolving, quickly adding 6.7415g of 2-methylimidazole, and violently stirring for 15 min; standing at room temperature overnight, centrifuging, washing thoroughly, and drying in vacuum drying oven at 60 deg.C for 12h to obtain ACs @ MOFs-ZIF-8.
(2) Preparation of ACs @ ZnO:
adding the ACs @ MOFs-ZIF-8 g (dry weight) prepared in the step (1) into a crucible, placing the crucible in a tube furnace, introducing argon for 30min, continuing to introduce the argon after completely removing air, raising the temperature at the speed of 5 ℃/min, keeping the temperature at 680 ℃ for 3h to completely carbonize the MOFs, continuing to introduce the argon, reducing the temperature at the speed of 10 ℃/min, stopping introducing the argon and starting to introduce oxygen after reducing the temperature to 320 ℃, keeping the temperature for 1.5h under the condition to completely oxidize the metal zinc, stopping introducing the oxygen, reducing the temperature to room temperature at the speed of 20 ℃/min, drying the metal zinc in a vacuum drying oven at 100 ℃ for 8h, wherein the number is ACs @ ZnO-9.
Example 10
(1) Preparing ACs @ MOFs-ZIF-5:
weighing 10.0579g of activated carbon (the particle size is between 600 and 800 mu m, and the specific surface area is 1497m 2 (ii)/g; pore volume of 3.85cm 3 /g) dissolved in 100mL of ethanol solution by ultrasonic dispersion, and after complete dispersion, 6.6802g of Zn (NO) is added under stirring 3 ) 2 ·6H 2 O, after dissolving, rapidly adding 1.8638g of terephthalic acid, and violently stirring for 15 min; placing the mixture into a hydrothermal reaction kettle, drying the mixture in an oven at 100 ℃ overnight, centrifuging the mixture completely, washing the mixture completely, and drying the mixture in a vacuum drying oven at 60 ℃ for 12 hours to obtain ACs @ MOFs-ZIF-5.
(2) Preparation of ACs @ ZnO:
adding the ACs @ MOFs-ZIF-5 5g (dry weight) prepared in the step (1) into a crucible, placing the crucible in a tube furnace, introducing argon for 30min, continuously introducing argon after air is completely removed, heating at the speed of 5 ℃/min, keeping at 650 ℃ for 3.5h to completely carbonize the MOFs, continuously introducing argon, cooling at the speed of 10 ℃/min, stopping introducing argon and starting introducing oxygen after the temperature is reduced to 300 ℃, keeping for 2h under the condition to completely oxidize the metal zinc, stopping introducing oxygen, cooling to room temperature at the speed of 20 ℃/min, drying in a vacuum drying oven at 100 ℃ for 8h, and numbering) ACs @ ZnO-10.
Comparative example 1
(1) Preparing ACs @ MOFs-ZIF-67:
weighing 10.5268g of activated carbon (the particle size is between 400 and 800 mu m, and the specific surface area is 1154 m) 2 (ii)/g; pore volume of 2.61cm 3 The mixture is dissolved in 100mL of ethanol solution by ultrasonic dispersion, and after the mixture is completely dispersed, 4.9806g of Co (NO) is added under stirring 3 ) 2 ·6H 2 O, after dissolving, quickly adding 6.7415g of 2-methylimidazole, and violently stirring for 15 min; standing at room temperature overnight, centrifuging, washing thoroughly, and drying in vacuum drying oven at 60 deg.C for 12h to obtain ACs @ MOFs-ZIF-67.
(2) Preparation of ACs @ CoO:
adding the ACs @ MOFs-ZIF-67 5g (dry weight) prepared in the step (1) into a crucible, placing the crucible in a tube furnace, introducing argon for 30min, after completely driving off air, continuously introducing argon, heating at the speed of 5 ℃/min, keeping at 680 ℃ for 3h to completely carbonize the MOFs, continuously introducing argon, cooling at the speed of 10 ℃/min, after cooling to 320 ℃, stopping introducing argon and starting introducing oxygen, keeping for 1.5h under the condition to completely oxidize the metal zinc, stopping introducing oxygen, cooling to room temperature at the speed of 20 ℃/min, drying in a vacuum drying oven at 100 ℃ for 8h, wherein the number is ACs @ CoO.
Comparative example 2
Preparation of ACs @ ZnO:
10.5268g of activated carbon (particle size of 400-800 μm, specific surface area of 1154 m) is weighed 2 (ii)/g; pore volume of 2.61cm 3 /g) dissolved in 100mL of methanol solution by ultrasonic dispersion, and after complete dispersion, 5.2648g of Zn (CH) was added under stirring 2 COO) 2 ·2H 2 0, stirring vigorously for 10min. Then 20mL of NaOH (2M) aqueous solution is added, after stirring for 5min, the solution is transferred to a high-pressure reaction kettle, and is kept at 100 ℃ for 5h, and is naturally cooled to room temperature. The resulting product was filtered by centrifugation, washed several times with distilled water and ethanol to remove ions that may remain in the final product, and finally dried in air at 60 ℃ for 12h, numbered) ACs @ ZnO.
Test example 1 static adsorption test of adsorbent for adsorbing urea in peritoneal fluid
Examples 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10 adsorbents ACs @ ZnO-1, ACs @ ZnO-2, ACs @ ZnO-3 ACs @ ZnO-4, ACs @ ZnO-5, ACs @ ZnO-6, ACs @ ZnO-7, ACs @ ZnO-8, ACs @ ZnO-9 and ACs @ ZnO-10 were experimental groups, comparative examples ACs @ CoO and ACs @ ZnO were control groups, 70mg each was taken in a centrifuge tube, 10mL of the peritoneal dialysis patient's peritoneal fluid (urea concentration in the sample was about 20 mmoL/L) was added, the seal film was sealed, and adsorption was performed in an air shaker at 37 ℃ for 2h with shaking. After the adsorption is finished, centrifuging at 1000rpm/min for 1min, centrifuging, and taking supernatant to measure the concentration of the supernatant.
The adsorption results are shown in figure 1.
As can be seen from FIG. 1, ten adsorbents of ACs @ ZnO-1, ACs @ ZnO-2, ACs @ ZnO-3, ACs @ ZnO-4, ACs @ ZnO-5, ACs @ ZnO-6, ACs @ ZnO-7, ACs @ ZnO-8, ACs @ ZnO-9 and ACs @ ZnO-10 in the examples all had urea removal rates of about 80%, which were significantly higher than those of comparative examples ACs @ CoO and ACs @ ZnO (40%), and were used as adsorbents for removing excess urea in peritoneal dialysis solutions.
Test example 2 evaluation of adsorbent cytotoxicity
The following experimental procedure for the in vitro cytotoxicity assay was used to assess the cytotoxicity of the adsorbents.
(1) Each 4g of the adsorbents ACs @ ZnO-1, ACs @ ZnO-2, ACs @ ZnO-3, ACs @ ZnO-4, ACs @ ZnO-5, ACs @ ZnO-6, ACs @ ZnO-7, ACs @ ZnO-8 and ACs @ ZnO-9 of examples 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10 was used as an experimental group, which was immersed in 20mL of DMEM medium containing 10% Fetal Bovine Serum (FBS) and 1% double antibody and extracted at 37 ℃ for 24 hours in a water bath.
(2) Fully cultured well-differentiated mouse embryonic fibroblasts (NIH 3T 3) in DMEM at 37 ℃ with 5% CO 2 Culturing in a cell incubator until the activity and the state of the cells are kept stable.
(3) NIH3T3 cells were seeded at a density of 1000 cells per well in 96-well plates and maintained for 24h.
(4) To evaluate the cytotoxicity of the adsorbents, after 24h of culture of the cells in 96-well plates, they were replaced by:
a: negative control: 100 μ L DMEM complete medium;
b: positive control: 100 μ L DMEM complete medium plus 5% dmso;
c: experimental groups: 100 μ L of ten kinds of adsorbents (ACs @ ZnO-1, ACs @ ZnO-2, ACs @ ZnO-3, ACs @ ZnO-4, ACs @ ZnO-5, ACs @ ZnO-6, ACs @ ZnO-7, ACs @ ZnO-8, ACs @ ZnO-9, and ACs @ ZnO-10).
(5) Placing the cells after medium replacement in a cell culture incubator (37 ℃,5% 2 ) And culturing for 72h.
(6) The cytotoxicity of the adsorbents was measured using a Cell Counting Kit-8 (CCK-8).
(7) Add 10. Mu.L of CCK-8 solution to each well, taking care.
(8) The plates were incubated in an incubator for 3h.
(9) The absorbance at 450nm was measured using a microplate reader.
(10) The relative proliferation rate (RGR) of NIH3T3 cells was calculated according to the following formula:
RGR＝X/X 0 ×100％
wherein X is the OD of the cells in the experimental group, X 0 Is the OD value of the blank control group, i.e., the OD value of NIH3T3 cells cultured in the normal complete medium.
The evaluation criteria for cytotoxicity were: the cytotoxicity level corresponding to the positive control group is at least 3, so that the accuracy of experimental operation is ensured, and if the cytotoxicity level corresponding to the positive control group is less than 3, the detection is required again, so that the accuracy of the experiment is ensured.
TABLE 1 cytotoxicity grading Table
The results are shown in FIG. 2.
As can be seen from fig. 2, the relative proliferation rate of the positive control was 24.9%, the toxicity rating was 4, and the positive control was at least 3. As can be seen from the figure, ten adsorbents of ACs @ ZnO-1, ACs @ ZnO-2, ACs @ ZnO-3, ACs @ ZnO-4, ACs @ ZnO-5, ACs @ ZnO-6, ACs @ ZnO-7, ACs @ ZnO-8, ACs @ ZnO-9 and ACs @ ZnO-10 in the examples have cytotoxicity grades of 1, and meet the cytotoxicity standards of biomedical materials.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and these modifications or substitutions do not depart from the spirit of the corresponding technical solutions of the embodiments of the present invention.
Claims (17)
1. An adsorbent for removing urea, which is prepared by the following method:
adding a carbon carrier in the process of preparing the Zn-ZIF metal organic framework material, wherein the mass ratio of the carbon carrier to an organic ligand precursor used for preparing the Zn-ZIF metal organic framework material is 10:1-10, sequentially carrying out high-temperature carbonization and low-temperature oxidation on the obtained carbon-doped Zn-ZIF metal organic framework material to obtain the adsorbent;
the carbon carrier is activated carbon;
the high-temperature carbonization is carried out under the condition of protective gas, the temperature is 600-800 ℃, and the time is 2-6h;
the low-temperature oxidation is carried out under the condition of oxygen at the temperature of 300-400 ℃ for 1-3 h;
the adsorbent for removing urea is used in peritoneal dialysis biomedical materials.
2. The adsorbent for removing urea according to claim 1, wherein the mass ratio of the carbon-based carrier to the organic ligand precursor used for preparing the Zn-ZIF metal organic framework material is 10:3-8.
3. Adsorbent for removing urea according to claim 1, characterized in that the particle size of said activated carbon is 200-1000 μm, the specific surface area is 500-1700 m/g, the pore volume is 0.95-4.68cm 3 /g。
4. The sorbent for the removal of urea according to claim 1, characterized in that the activated carbon has a particle size of 400-800 μm and a specific surface area of 800-1500m 2 Per g, pore volume of 1.26-3.89cm 3 /g。
5. The sorbent for urea removal according to any one of claims 1 to 4, characterized in that the high temperature carbonization is carried out under protective gas conditions at a temperature of 650 to 750 ℃ for a time of 2.5 to 4.5 h.
6. The sorbent for removal of urea as claimed in claim 1 wherein the time of low temperature oxidation is 1.5-2.5h.
7. Method for preparing an adsorbent for urea removal according to any one of claims 1-6, characterized in that it comprises the following steps:
(a) Dispersing a carbon-based carrier in an alcohol solvent;
(b) Dissolving a zinc source in (a);
(c) Pouring the organic ligand precursor solution into the step (b), and mixing;
(d) Standing the solution obtained in the step (c) at room temperature overnight, or putting the solution into a hydrothermal reaction kettle, heating the solution overnight, separating, washing and drying the solution;
(e) After drying is finished, carrying out high-temperature carbonization under the condition of protective gas;
(f) After carbonization is finished, low-temperature oxidation is carried out;
(g) And (4) drying in vacuum to obtain the adsorbent.
8. The production method according to claim 7, wherein the mass ratio of the carbon-based carrier to the organic ligand precursor is 10:3-8.
9. The method according to claim 7, wherein the concentration of the carbon-based carrier is 10 to 20 mg/mL.
10. The preparation method according to claim 7, wherein the Zn-ZIF-like organic framework material is ZIF-8.
11. Preparation method according to claim 7, characterized in that the activated carbon has a particle size of 200-1000 μm, a specific surface area of 500-1700 m/g, a pore volume of 0.95-4.68 cm/g 3 /g。
12. The method according to claim 7, wherein the activated carbon has a particle size of 400 to 800 μm and a specific surface area of 800 to 1500m 2 Per g, pore volume of 1.26-3.89cm 3 /g。
13. The method according to any one of claims 7 to 12, wherein the temperature of the high-temperature carbonization in the step (e) is 650 to 750 ℃ for 2.5 to 4.5 hours.
14. The method according to any one of claims 7 to 12, wherein the time for the low-temperature oxidation in the step (f) is 1.5 to 2.5 hours.
15. The process according to any one of claims 7 to 12, wherein the temperature of the vacuum drying in step (g) is 60 to 100 ℃ for 6 to 12 hours.
16. The method according to any one of claims 7 to 12, wherein the vacuum drying is carried out at a temperature of 80 to 100 ℃ for a time of 8 to 10 hours.
17. An adsorption device comprising the adsorbent for urea removal according to any one of claims 1 to 6.
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