CN114733453B - Monolithic nitrogen-doped carbon catalytic material with multi-stage porous structure, preparation method and application thereof - Google Patents
Monolithic nitrogen-doped carbon catalytic material with multi-stage porous structure, preparation method and application thereof Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
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- B01J20/28047—Gels
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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Abstract
An integral catalytic material with a self-supporting multi-stage porous structure, a 3D printing preparation method and application thereof belong to the technical field of adsorption catalytic materials. The nitrogen-doped carbon hydrogel precursor is used as an ink main body for 3D printing, a multistage porous structure model suitable for continuous treatment of flowing wastewater is designed by utilizing three-dimensional modeling software, and then the 3D printing integral nitrogen-doped carbon aerogel is prepared by a 3D printing technology of direct ink writing. The integral aerogel has good continuous adsorption catalysis performance on sewage in a flowing state, has the characteristics of low cost, simple operation, good stability and large-scale preparation, and has better recoverability, sustainability and industrialized application prospect in the field of environmental sewage purification.
Description
Technical Field
The invention belongs to the technical field of adsorption catalytic materials, and particularly relates to an integral catalytic material with a self-supporting multi-stage porous structure, a 3D printing preparation method and application of the integral catalytic material in sewage purification.
Background
With the acceleration of the industrialization process and the rapid development of science and technology, the pollution of organic pollutants and bacteria to the water environment seriously harms the ecological environment and human health, and has attracted global attention. The advanced oxidation method, which can degrade organic matters and inactivate bacteria by generating high active oxygen, is one of the most effective wastewater treatment methods. Advanced oxidation processes based on peroxymonosulfates produce active oxygen species, such as SO, with higher redox potentials and relatively longer half-lives 4 - And 1 O 2 and the treatment of refractory organic matters and bacteria in water has greater potential. Nitrogen-doped carbon materials, which have high stability and fast electron transport properties, are promising catalytic materials, but need further modification to improve performance. In addition, most of the traditional catalysts are in a powder state on a macroscopic scale, are easy to agglomerate in practical application to reduce the activity of the traditional catalysts, and have poor recyclability and undesirable industrialization prospect. The problem of continuously treating the flowing wastewater in practical application is also urgently solved.
In recent years, three-dimensional carbon materials having a porous structure and self-supporting properties have been receiving increasing attention from researchers due to their numerous advantages. Teaching team of Zhongzheng (ACS applied materials)&interfaces,2019,11, 34222-34231) adopts a hydrothermal synthesis and directional freezing method to design and manufacture a vertically oriented anisotropic CoFe 2 O 4 @ graphene composite aerogel. Due to the long and straight pore channel structure, the Peroxymonosulfate (PMS) can be effectively activated under the flowing condition, and various organic pollutants such as indigo carmine, phenol and the like can be continuously and efficiently degraded. The Nano porous carbon foam is prepared by an easy-to-operate salt-assisted pyrolysis method by an ACS Applied Nano Materials (2020, 3, 1564-1570) and by a green method taking edible raw Materials (such as agar, pectin and flour) as raw Materials. And the air filter paper is combined with non-woven fabric to form composite air filter paperTo PM 2.5 And PM 10 Has excellent adsorption and filtration performance. Researches show that the porous structure of the monolithic carbon aerogel is beneficial to improving the adsorption and catalysis efficiency and improving the stability, but the current method for preparing the green monolithic carbon aerogel in a large scale is limited.
The natural carbon source such as agarose is a non-toxic and cheap natural polysaccharide material, the physical property of the natural carbon source can change along with the temperature, the natural carbon source has better gel property, and the hydrogel has certain mechanical strength and the advantages of natural biomaterials. In recent years, the emerging 3D printing technology can optimize the catalytic and adsorption properties of the composite material by accurately controlling the material structure and component distribution, is simple and flexible to operate, and can prepare the catalyst with a complex integral three-dimensional structure more efficiently. However, hydrogels based on natural carbon sources, such as pure agar, lack the appropriate mechanical properties and generally have poor formability properties. So far, no report for preparing the monolithic adsorption catalytic material based on the natural carbon source by 3D printing exists.
Disclosure of Invention
The invention aims to provide an integral nitrogen-doped carbon catalytic material with a self-supporting multi-stage porous structure, a 3D printing preparation method and application thereof in sewage purification. The 3D printing integral nitrogen-doped carbon aerogel has a self-supporting millimeter-micron-nanometer multi-stage porous structure, can improve the utilization efficiency of a specific surface area and an active site, optimizes a mass transfer process, and is favorable for water circulation and adsorption of organic pollutants and bacteria. The natural carbon source is cheap and easy to obtain, accords with the concept of green environmental protection, and is suitable for being widely applied to the field of sewage treatment. The integral nitrogen-doped carbon aerogel prepared by applying the 3D printing technology has good adsorption catalysis performance, operability and structural stability, can be simply prepared in a large scale, and has a very wide industrial application prospect in sewage treatment.
The invention discloses a preparation method of a 3D printing integral nitrogen-doped carbon aerogel with a self-supporting multistage porous structure, which comprises the following specific steps:
1) Adding 0.5-2.0 g of salt sacrificial template into 5-20 mL of deionized water, then sequentially and slowly adding 0.2-2.0 g of nitrogen source and 0.2-1.0 g of natural carbon source respectively, continuously stirring at the rotating speed of 500-800 rpm during the period, and heating the reaction system to 60-90 ℃ after adding the carbon source; after the raw materials are completely dissolved, slowly adding a rheological regulator with the dosage of 2-15 wt% of deionized water, closing heating after the raw materials are completely dissolved, and continuously stirring until the solution is cooled to room temperature to obtain a nitrogen-doped carbon hydrogel precursor with 3D printing adaptability;
2) Designing a latticed structure model of the monolithic catalyst suitable for continuous treatment of the flowing wastewater by using three-dimensional modeling software (such as Solidwork, cinema 4D, 3DS Max, rhinocero and the like), introducing the established model into 3D printing software (such as RepperHost, simplify3D, slic3r, 3DXpert and the like) in a configuration computer of Direct Ink Writing (DIW) printing equipment, and setting appropriate printing parameters: the layer height = needle diameter × 0.6-0.9, the layer number = 3-30, the filling degree =15% -40%, the speed = 2-15 mm/s;
3) Placing the nitrogen-doped carbon hydrogel precursor cooled to room temperature obtained in the step 1) into a disposable syringe needle cylinder, centrifuging for 2-10 min to remove bubbles, connecting the needle cylinder with 18, 20, 22 or 25-gauge printing needles (the diameters of the 18, 20, 22 and 25-gauge needles are respectively 0.84mm, 0.60mm, 0.41mm and 0.26 mm) and adding the needle cylinder to Direct Ink Writing (DIW) printing equipment; printing on an acrylic plate, quickly freezing by pouring liquid nitrogen after printing is finished, and keeping the shape to the maximum extent to obtain a 3D printing hydrogel sample;
4) Carrying out vacuum freeze drying on the 3D printing hydrogel sample obtained in the step 3), converting the hydrogel into aerogel, and then pyrolyzing the aerogel in a tubular furnace at 500-1000 ℃ for 0.5-2 h in an inert atmosphere; after pyrolysis is finished, stirring and washing by using a large amount of deionized water to remove crystal particles of the salt sacrificial template existing in the material obtained by pyrolysis; and finally, drying the printed sample overnight to obtain the 3D printed integral nitrogen-doped carbon aerogel with the self-supporting multistage porous structure.
The salt sacrificial template in the step 1) is one of sodium chloride, sodium nitrate and the like;
the nitrogen source in the step 1) is one of urea, melamine and the like;
the natural carbon source material in the step 1) is one of natural polymer materials such as agarose, pectin, gelatin, chitosan, sodium alginate, cellulose derivatives and the like;
the rheological regulator in the step 1) is one of hydroxypropyl methylcellulose (HPMC), hydroxypropyl cellulose, hydroxyethyl cellulose, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, nano clay and the like.
The temperature of the vacuum freeze drying in the step 4) is-40 to-80 ℃, and the vacuum freeze drying time is 2 to 72 hours; the drying temperature is 40-90 ℃, and the drying time is 2-48 h.
The method takes natural polymer coordination compound hydrogel containing a salt sacrificial template and a nitrogen source as 3D printing ink, utilizes three-dimensional modeling software to design a channel-shaped bracket structure model, and then uses a Direct Ink Writing (DIW) technology to perform 3D printing, so that the integrated nitrogen-doped carbon aerogel with a three-dimensional self-supporting multistage porous structure is prepared, and further the method is used for the research of activating PMS to continuously inactivate bacteria and degrade organic pollutants under a flowing condition. Continuous treatment experiments of flowing wastewater show that the integral nitrogen-doped carbon aerogel disclosed by the invention has excellent continuous degradation and sterilization performances. When the flow velocity in the flow type wastewater treatment device is 60mL h -1 In the process, the degradation rate of the integral nitrogen-doped carbon aerogel on rhodamine B (RhB) can reach 97.2% within 5min, the degradation rate can be stabilized to about 91.9% after continuous operation for 5 hours, and the sterilization rate of 100% on escherichia coli can be continuously maintained for at least 5 hours. When the flow rate of the waste water is 120mL h -1 In the process, the degradation rate of the integral nitrogen-doped carbon aerogel on RhB can reach 96.5% within 5min, the integral nitrogen-doped carbon aerogel can be stabilized to about 89.7% after running for 3h, and the 100% sterilization rate on escherichia coli can be maintained for at least 3h. The integral nitrogen-doped carbon aerogel has the characteristics of low cost, simple operation, good stability and large-scale preparation, has better recoverability in the field of environmental sewage purification, and can be continuously and industrially appliedThe prospect of (1).
Drawings
FIG. 1: a camera photograph of the monolithic nitrogen-doped carbon aerogel sample prepared in example 1 was 3D printed; fig. 1 (a) is a photograph of a 3D printed cylindrical grid-like hydrogel after vacuum freeze-drying (not pyrolyzed); FIG. 1 (b) is a photograph of the sample of FIG. 1 (a) after pyrolysis and washing and drying; FIG. 1 (c) is a schematic diagram of the use of the sample of FIG. 1 (b) in a multi-layer stack in a flow device (disposable syringe); FIG. 1 (d) is a photograph of a side view of the sample of FIG. 1 (a).
FIG. 2: scanning electron micrographs (fig. 2 (a) and 2 (b)) and transmission electron micrographs (fig. 2 (c)) of the 3D-printed monolithic nitrogen-doped carbon aerogel prepared in example 1; from fig. 2 (a) to fig. 2 (c), the magnification is increased in order.
Fig. 3 (a): at 10ppm of RhB solution and 1g L -1 Under the condition that the PMS solution flows simultaneously, the 3D printing integral nitrogen-doped carbon aerogel prepared in the embodiment 1 prints a real-time (0-300 min) ultraviolet-visible absorption spectrum diagram of the rhodamine B solution; FIG. 3 (b) is a real-time degradation rate curve of 3D printed integral nitrogen-doped carbon aerogel and non-3D printed bulk nitrogen-doped carbon to RhB solution, wherein curve 1 is the 3D printed integral nitrogen-doped carbon aerogel when the solution flow rate is 60mL h -1 The degradation rate curve of (1), curve 2 is that the 3D printing integral nitrogen-doped carbon aerogel has a solution flow rate of 120mL h -1 Curve 3 is the flow rate of the bulk nitrogen-doped carbon for non-3D printing at a solution flow rate of 60mL h -1 Curve 4 is the flow rate of the bulk nitrogen-doped carbon not printed in 3D at a solution flow rate of 120mL h -1 Degradation rate curve of (d).
FIG. 4 is a schematic view of: in the bacterial liquid concentration of 10 6 CFU mL -1 PMS concentration of 1g L -1 Flow rate of 60mL h -1 Under the conditions of (1), the 3D printed integral nitrogen-doped carbon aerogel prepared in example 1 continuously processes a colony formation experiment camera picture of flowing escherichia coli liquid. FIGS. 4 (a) to 4 (i) show flow periods of (a) 5min, (b) 15min, (c) 30min, (d) 60min, (e) 90min, (f) 120min, (g) 180min, (h) 240min and (i) 300min, respectively. FIG. 4 (j) is a blank control (pure bacterial broth culture) without catalyst and PMS.
FIG. 5: in thatBacterial liquid concentration of 10 7 CFU mL -1 PMS concentration of 1g L -1 The flow rate is 120mL h -1 3D printed monolithic nitrogen-doped carbon aerogel prepared in example 1 was continuously processed into a colony formation experiment camera picture of flowing escherichia coli liquid. FIGS. 5 (a) to 5 (e) show the flow periods of (a) 5min, (b) 30min, (c) 60min, (d) 120min and (e) 180min, respectively. FIG. 5 (f) is a blank (pure bacterial culture in solution) without catalyst and PMS.
FIG. 6: scanning electron micrograph of 3D printed monolithic nitrogen-doped carbon aerogel material prepared in example 1 after flowing degradation RhB reaction: fig. 6 (b) is a high magnification view of fig. 6 (a).
FIG. 7: a camera photograph of the monolithic nitrogen-doped carbon aerogel prepared in example 2 was printed in 3D; FIG. 7 (a) is a photograph of a 3D printed square grid-like hydrogel before vacuum freeze-drying; FIG. 7 (b) is a photograph of the sample of FIG. 7 (a) after vacuum freeze-drying (left) and a photograph of a side view (right); fig. 7 (c) is a photograph of the final morphology of the sample of fig. 7 (b) after completion of pyrolysis.
Detailed Description
The technical solution of the present invention is described in more detail by the following specific implementation examples, which are not to be construed as limiting the present invention.
Example 1
1) First, 0.8g of sodium chloride was added to a beaker containing 20mL of deionized water, and then 0.8g of urea and 0.4g of agarose were slowly added to the above solution in sequence, while stirring was continued at 600rpm, and the temperature was raised to 80 ℃ during the agarose addition. After complete dissolution, 5wt% (compared to 20mL of deionized water) of HPMC was slowly added, and after complete dissolution, heating was turned off but stirring was continued until the solution cooled to room temperature, to obtain an N-doped carbohydrate gel precursor with 3D printability.
2) Referring to characteristic parameters of a typical wastewater pipeline, a micro pipeline is simulated by using a 10mL disposable syringe tube, and by combining the characteristics of 3D printing, an integral multi-stage porous structure model (cylinder shape, diameter multiplied by height: 1.9cm × 1.0 cm). Then, the established model is led into 3D printing software RepperHost in a DIW printer configuration computer, and Slic3r embedded in the software is used for setting printing parameters: layer height (0.35mm, 22 gauge needle diameter × 0.85), number of layers (15), degree of filling (20%), speed (5 mm/s).
3) Placing the hydrogel precursor obtained in the step 1) into a disposable syringe, centrifuging for 5min to remove bubbles, connecting the syringe with a No. 22 printing needle, and installing the syringe on a 3D printing device. Thereafter, the printing interface of the software is opened, and printing can be started by dot "Print" after setting the appropriate extrusion parameters (Print flow: 10%). The samples were printed on acrylic plates and after printing the freezing was rapidly completed by pouring liquid nitrogen.
4) Transferring the 3D printing sample obtained in the step 3) to a vacuum freeze dryer, freeze-drying at-40 ℃ for 36 hours, and then pyrolyzing at 800 ℃ for 1 hour in a tubular furnace under nitrogen atmosphere. After pyrolysis was completed, the removed material was washed with a large amount of deionized water with stirring to remove NaCl crystal particles present in the material. Then, the obtained product is placed in an electrothermal blowing dry box to be dried overnight at 60 ℃, and finally the 3D printing integral nitrogen-doped carbon aerogel with self-supporting property is obtained.
Example 1 Performance testing
In the case where the concentration of the RhB aqueous solution was 10ppm and the concentration of the PMS aqueous solution was 1g L -1 Under the condition of (1), the total volume is 60mL h -1 、120mL h -1 The flow rate of (a) was input into the mixed solution of RhB and PMS (RhB and PMS were respectively placed in 2 separatory funnels, reacted and then mixed together to flow through the aerogel) and passed through the 3D printed monolithic nitrogen doped carbon aerogel, the reacted solution was withdrawn at the same flow rate, and the uv-visible spectrum was measured on the withdrawn reaction solution at time intervals set as curves 1 and 2 of fig. 3 (b). The real-time efficiency of continuous degradation of flowing organic pollutants by 3D-printed monolithic nitrogen-doped carbon aerogel activated PMS was evaluated by analyzing the change in the characteristic absorption peak area of RhB in the reaction solution in the uv-visible absorption spectrum (λ =554nm at the characteristic absorption peak).
The degradation rate (D) is calculated by the formula:
D＝(A 0 -A)/A×100％
wherein D is the degradation rate of RhB at each set time point in the reaction, A 0 The integral area of the characteristic peak of the RhB when the degradation is not carried out is shown, and A is the integral area of the characteristic peak of the RhB at each set time point after the degradation of the integral nitrogen-doped carbon aerogel printed by 3D or the nitrogen-doped carbon printed by non-3D.
Secondly, escherichia coli is selected as a research object, and the flow type sterilization performance of the 3D printing integral nitrogen-doped carbon aerogel is researched through a colony forming experiment and a flat plate colony counting method. The concentration of the bacterial solution is 10 6 The concentration of the CFU and PMS solution is 1g L -1 The flow rate of the PMS and the bacteria mixed solution (the bacteria solution and the PMS solution are respectively filled in 2 separating funnels and are mixed together to flow through the aerogel after the reaction is started) is 60mL h -1 Under the condition of (3), continuously treating flowing bacteria liquid for 5min, 15min, 30min, 60min, 90min, 120min, 180min, 240min and 300min respectively in 3D printing of the integral bionic nitrogen-doped carbon aerogel, extracting the reacted bacteria liquid, and coating the bacteria liquid on an LB solid culture medium for 12h of constant-temperature culture for evaluating the sterilization effect.
Solubility in bacteria of 10 7 The concentration of the CFU and PMS solution is 1g L -1 The flow rate of the PMS and the bacteria mixed solution (the bacteria solution and the PMS solution are respectively filled in 2 separating funnels and are mixed together to flow through the aerogel after the reaction is started) is 120mL h -1 Under the condition, the flowing bacteria liquid is continuously processed for 5min, 30min, 60min, 120min and 180min after 3D printing of the integral nitrogen-doped carbon aerogel, the reacted bacteria liquid is extracted and coated on an LB solid culture medium for constant-temperature culture for 12h, and the constant-temperature culture is used for evaluating the sterilization effect.
As shown in fig. 1, the 3D printed monolithic nitrogen-doped carbon aerogel prepared in example 1 has a self-supportable millimeter-micron-nanometer multi-stage porous structure, and the monolithic catalyst has a macroscopically designed latticed structure facilitating water circulation, presenting a long cylindrical shape simulating a wastewater discharge pipe (fig. 1 (a), (D)), demonstrating that the hydrogel precursor has good printability. And no significant deformation occurred after the completion of the post-treatment operations such as vacuum freeze-drying, pyrolysis and washing, compared with the initial (fig. 1 (b)), indicating that the material also has good shape-retaining ability. In addition, as shown in fig. 1 (c), the 3D printed monolithic nitrogen-doped carbon aerogel can be stacked together for use in practical applications according to requirements, which indicates that it has good operability to meet complex application conditions.
As shown in fig. 2, as the magnification of the 3D printed monolithic nitrogen-doped carbon aerogel is increased from low to high, a millimeter-scale channel-shaped structure constructed by 3D printing can be observed, and the mesh-shaped pore diameter of the channel-shaped structure is about 1mm (fig. 2 (a)); 3D printing of the micro-scale pore structure formed after freeze-drying of the extruded hydrogel precursor, with an average size between 15 and 80nm (FIG. 2 (b)); and nano-porosity generated by NaCl as sacrificial template, wherein the nano-porosity is a circular pore structure with uniform shape and distribution, and the average size is between 150 nm and 250nm (FIG. 2 (c)).
As shown in FIG. 3, the RhB solution concentration was 10ppm and the PMS solution concentration was 1g L -1 The flow rate of the mixed solution is 60mL h -1 The absorbance of RhB solution flowing through the 3D printed monolithic nitrogen doped carbon aerogel for 5min dropped rapidly at the characteristic absorption peak (fig. 3 (a)). According to the degradation rate calculation formula, the 3D printed monolithic nitrogen-doped carbon aerogel can reach a degradation rate of 97.2% in the first 5min of continuous catalytic degradation RhB, and can still maintain a degradation rate of 91.9% after continuous reaction for 300min (fig. 3 (b) curve 1). In addition, the solution flow rate was 120mL h -1 Under the condition (b), the 3D printed monolithic nitrogen-doped carbon aerogel can reach a degradation rate of 96.5% in the first 5min of continuous catalytic degradation of RhB, and the degradation rate of RhB after continuous reaction for 180min can be stabilized at 89.7% (fig. 3 (b) curve 2). It is shown that the 3D printed monolithic nitrogen doped carbon aerogel prepared in example 1 has excellent sustained degradation performance on flowing RhB. Subsequently, the same continuous catalytic degradation RhB experiment was performed on the control sample, non-3D printed nitrogen-doped carbon, and assay analysis was performed on the withdrawn reaction solution at time intervals set as curves 3 and 4 of fig. 3 (b). It was found that the solution flow rate was 60mL h -1 Under the condition (1), the degradation rate of RhB within the first 5min is 77.6%. Continuing to react, the nitrogen-doped carbon which is not printed by 3D printing can be washed away under the washing of water flow to gradually block the filter membrane at the bottom end of the injector, and finally the reaction solution is difficult to be miniaturized after 60minThe degradation rate of RhB also dropped significantly to 62.7% when pumped out by the peristaltic pump (fig. 3, curve 3). At a solution flow rate of 120mL h -1 Under the condition (1), the degradation rate of the non-3D printed nitrogen-doped carbon to the RhB within 5min can only reach 62.8%, and the degradation rate of the RhB after 60min is greatly reduced to 56.1% (curve 4 in FIG. 3).
As shown in fig. 4, almost all colonies on the culture medium were observed after the bacterial solution coating culture without passing through the 3D printed monolithic nitrogen-doped carbon aerogel (fig. 4 (j)), and no colony growth on the culture medium was observed after passing through the bacterial solution coating culture for 5-300 min after the 3D printed monolithic nitrogen-doped carbon aerogel (fig. 4 (a) to fig. 4 (i)).
As shown in fig. 5, almost all colonies were observed on the culture medium after the bacterial solution coating culture without the 3D-printed monolithic nitrogen-doped carbon aerogel (fig. 5 (f)), and no colony growth was observed on the culture medium after the bacterial solution coating culture with the 3D-printed monolithic nitrogen-doped carbon aerogel for 5 to 180min (fig. 5 (a) to 5 (e)).
As shown in fig. 6, after the 3D printing integral nitrogen-doped carbon aerogel prepared in example 1 is subjected to the flow degradation RhB reaction, the millimeter-scale macroscopic appearance of the aerogel is basically unchanged, and further amplification of the aerogel can observe that the microscopic micro-nano porous structure of the aerogel is also maintained perfectly.
Example 2
The operations were performed in the same manner as in example 1, except that the structural model designed by the three-dimensional modeling software Solidwork in step 2) of example 1 was a rectangular parallelepiped shape (length × width × height: 2cm × 2cm × 1 cm), the printing parameters set in the 3D printing software repetiershot are unchanged: layer height (0.35mm, 22 gauge needle diameter × 0.85), number of layers (15), degree of filling (20%), speed (5 mm/s). And further adopting the same printing and post-treatment method to prepare the square-column-shaped 3D printing integral nitrogen-doped carbon aerogel, wherein the macroscopic millimeter-scale latticed pore diameter is about 1mm.
Fig. 7 is a camera photograph of the 3D printed monolithic nitrogen-doped carbon aerogel obtained in this example. The square column grid-shaped integral nitrogen-doped carbon aerogel is prepared as shown in the figure.
Example 3
The operations in the steps of embodiment 1 are the same except that the printing parameters set in the 3D printing software RepetierHost in step 2) of embodiment 1 are changed to: layer height (0.35mm, 22 gauge needle diameter × 0.85), number of layers (15), degree of filling (20%), speed (10 mm/s). The prepared 3D printing integral nitrogen-doped carbon aerogel in the shape of a cylinder has a macroscopic millimeter-scale grid pore size of about 1mm.
Example 4
The procedure was as in example 1 except that:
1) The addition amount of HPMC in step 1) of example 1 was 4wt%;
2) The printing parameters set in the 3D printing software RepetierHost in step 2) of embodiment 1 are changed to: layer height (0.35mm, 22 gauge needle diameter × 0.85), number of layers (10), degree of filling (20%), speed (5 mm/s);
3) The extrusion parameters set in step 3) of example 1 were changed to print flow:5% of the prepared 3D printing integral nitrogen-doped carbon aerogel in the shape of a cylinder, wherein the macroscopic latticed pore diameter is about 0.9mm.
Claims (8)
1. A preparation method of a 3D printing integral nitrogen-doped carbon aerogel with a self-supporting multistage porous structure comprises the following steps:
1) Adding 0.5-2.0 g of a salt sacrificial template into 5-20 mL of deionized water, then sequentially and slowly adding 0.2-2.0 g of a nitrogen source and 0.2-1.0 g of a natural carbon source into the deionized water respectively, continuously stirring at a rotating speed of 500-800 rpm during the process, and heating a reaction system to 60-90 ℃ after the carbon source is added; after the raw materials are completely dissolved, slowly adding a rheological regulator which accounts for 2-15 wt% of the dosage of the deionized water, after the raw materials are completely dissolved, closing and heating, and continuously stirring until the solution is cooled to room temperature to obtain a nitrogen-doped carbon hydrogel precursor with 3D printing adaptability; the salt sacrificial template is one of sodium chloride and sodium nitrate; the nitrogen source is one of urea and melamine;
2) Designing a latticed structure model of the monolithic catalyst suitable for continuous treatment of the flowing wastewater by using three-dimensional modeling software, introducing the established model into 3D printing software configured in a computer of Direct Ink Writing (DIW) printing equipment, and setting appropriate printing parameters: the layer height = the diameter of the needle head multiplied by 0.6 to 0.9, the layer number =3 to 30, the filling degree =15 to 40%, and the speed =2 to 15mm/s;
3) Placing the nitrogen-doped carbon hydrogel precursor cooled to room temperature obtained in the step 1) into a disposable syringe barrel, centrifuging for 2-10 min to remove air bubbles, connecting the syringe barrel with a number 18, 20, 22 or 25 printing needle head, and adding the syringe barrel on direct ink writing and printing equipment; printing on an acrylic plate, quickly freezing by pouring liquid nitrogen after printing is finished, and keeping the shape to the maximum extent so as to obtain a 3D printing hydrogel sample; 18. the diameters of the No. 20, no. 22 and No. 25 printing needles are 0.84mm, 0.60mm, 0.41mm and 0.26mm respectively;
4) Vacuum freeze drying the 3D printing hydrogel sample obtained in the step 3), converting the hydrogel into aerogel, and pyrolyzing for 0.5 to 2 hours at 500 to 1000 ℃ in an inert atmosphere; after pyrolysis is finished, stirring and washing by using a large amount of deionized water to remove crystal particles of the salt sacrificial template existing in the material obtained by pyrolysis; finally, the printed sample was dried overnight, resulting in a 3D printed monolithic nitrogen-doped carbon aerogel with a self-supporting multi-stage porous structure.
2. The method for preparing a 3D-printable monolithic nitrogen-doped carbon aerogel having a self-supporting multi-stage porous structure according to claim 1, wherein: the natural carbon source material in the step 1) is one of agarose, pectin, gelatin, chitosan, sodium alginate and cellulose derivatives.
3. The method for preparing a 3D-printable monolithic nitrogen-doped carbon aerogel having a self-supporting multi-stage porous structure according to claim 1, wherein: the rheological regulator in the step 1) is one of hydroxypropyl methylcellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane and nano clay.
4. The method for preparing a 3D-printable monolithic nitrogen-doped carbon aerogel having a self-supporting multi-stage porous structure according to claim 1, wherein: the three-dimensional modeling software in the step 2) is one of Solidwork, cinema 4D, 3DS Max and Rhinocero; the 3D printing software is one of RepetierHost, simplify3D, slic3r and 3 DXpert.
5. The method for preparing a 3D-printable monolithic nitrogen-doped carbon aerogel having a self-supporting multi-stage porous structure according to claim 1, wherein: the temperature of the vacuum freeze drying in the step 4) is-40 to-80 ℃, and the vacuum freeze drying time is 2 to 72 hours.
6. The method for preparing a 3D-printable monolithic nitrogen-doped carbon aerogel having a self-supporting multi-stage porous structure according to claim 1, wherein: the drying temperature in the step 4) is 40-90 ℃, and the drying time is 2-48 h.
7. The utility model provides a 3D prints integral nitrogen-doped carbon aerogel with can self-supporting multistage porous structure which characterized in that: is prepared by the process according to any one of claims 1 to 6.
8. Use of the 3D printed monolithic nitrogen-doped carbon aerogel with a self-supportable multi-stage porous structure of claim 7 in sewage purification.
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