CN114733453A - 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
- Publication number
- CN114733453A CN114733453A CN202210561326.6A CN202210561326A CN114733453A CN 114733453 A CN114733453 A CN 114733453A CN 202210561326 A CN202210561326 A CN 202210561326A CN 114733453 A CN114733453 A CN 114733453A
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- printing
- doped carbon
- porous structure
- self
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 230000003197 catalytic effect Effects 0.000 title abstract description 13
- 239000004966 Carbon aerogel Substances 0.000 claims abstract description 58
- 238000010146 3D printing Methods 0.000 claims abstract description 43
- 239000000017 hydrogel Substances 0.000 claims abstract description 19
- 239000004964 aerogel Substances 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 239000010865 sewage Substances 0.000 claims abstract description 8
- 239000002351 wastewater Substances 0.000 claims abstract description 8
- 238000000746 purification Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 23
- 238000007639 printing Methods 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000000197 pyrolysis Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 229920000936 Agarose Polymers 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 5
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 5
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 5
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 2
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 2
- 229920001661 Chitosan Polymers 0.000 claims description 2
- 108010010803 Gelatin Proteins 0.000 claims description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 241000282806 Rhinoceros Species 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 239000012802 nanoclay Substances 0.000 claims description 2
- 239000001814 pectin Substances 0.000 claims description 2
- 235000010987 pectin Nutrition 0.000 claims description 2
- 229920001277 pectin Polymers 0.000 claims description 2
- 239000000661 sodium alginate Substances 0.000 claims description 2
- 235000010413 sodium alginate Nutrition 0.000 claims description 2
- 229940005550 sodium alginate Drugs 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 35
- 230000015556 catabolic process Effects 0.000 description 26
- 238000006731 degradation reaction Methods 0.000 description 26
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 26
- 229940043267 rhodamine b Drugs 0.000 description 26
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 17
- 241000894006 Bacteria Species 0.000 description 14
- 239000000523 sample Substances 0.000 description 12
- 230000001580 bacterial effect Effects 0.000 description 9
- 239000011148 porous material Substances 0.000 description 8
- 239000001963 growth medium Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000001954 sterilising effect Effects 0.000 description 6
- 238000004659 sterilization and disinfection Methods 0.000 description 6
- 241000588724 Escherichia coli Species 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000002957 persistent organic pollutant Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000005757 colony formation Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 229920005615 natural polymer Polymers 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 1
- 238000009631 Broth culture Methods 0.000 description 1
- 229910002518 CoFe2O4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 230000001332 colony forming effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- KHLVKKOJDHCJMG-QDBORUFSSA-L indigo carmine Chemical compound [Na+].[Na+].N/1C2=CC=C(S([O-])(=O)=O)C=C2C(=O)C\1=C1/NC2=CC=C(S(=O)(=O)[O-])C=C2C1=O KHLVKKOJDHCJMG-QDBORUFSSA-L 0.000 description 1
- 229960003988 indigo carmine Drugs 0.000 description 1
- 235000012738 indigotine Nutrition 0.000 description 1
- 239000004179 indigotine Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000007158 vacuum pyrolysis Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
-
- 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
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
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 thereof 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 substances 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 oxidation-reduction potentials and relatively longer half-lives4 -And1O2and 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 still need further modification to improve performance. In addition, it is largeMost traditional catalysts are in a powder state in a macroscopic view, and are easy to agglomerate in practical application to reduce the activity of the catalysts, and the catalysts are poor in recyclability and have unsatisfactory industrialization prospects. The problem of continuously treating the flowing and discharged 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. In the middle school teaching team (ACS applied materials)&interfaces,2019,11,34222-34231) adopts a hydrothermal synthesis and directional freezing method to design and manufacture a vertically-oriented anisotropic CoFe2O4@ 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 Huangfuqiang professor group (ACS Applied Nano Materials,2020,3, 1564-. And the PM and non-woven fabric are combined into composite air filter paper for PM2.5And PM10Has 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 performances of the composite material by accurately controlling the material structure and component distribution, is simple, convenient 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 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 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 respectively, continuously stirring at a rotating speed of 500-800 rpm during the period, and heating a 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 a Direct Ink Writing (DIW) printing device, and setting appropriate printing parameters: the layer height is equal to the diameter of the needle head multiplied by 0.6-0.9, the layer number is equal to 3-30, the filling degree is equal to 15% -40%, and the speed is equal to 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, centrifuging for 2-10 min to remove bubbles, connecting the syringe with 18, 20, 22 or 25-gauge printing needles (the diameters of the 18, 20, 22 and 25-gauge needles are 0.84mm, 0.60mm, 0.41mm and 0.26mm respectively) and adding the syringe 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 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; finally, the printed sample is dried overnight, so as to obtain the 3D printed monolithic nitrogen-doped carbon aerogel with the self-supporting multi-stage 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 invention takes natural polymer coordination compound hydrogel containing salt sacrificial template and nitrogen source as 3D printing ink, designs a channel-shaped bracket structure model by using three-dimensional modeling software, and then writes by using direct ink (DIW) technology, and preparing the integral nitrogen-doped carbon aerogel with a three-dimensional self-supporting multi-stage porous structure, so that the research on activating PMS to continuously inactivate bacteria and degrading organic pollutants under a flowing condition is realized. Continuous treatment experiments of flowing wastewater show that the integral nitrogen-doped carbon aerogel disclosed by the invention has excellent continuous degradation and sterilization performance. When the flow velocity in the flow type wastewater treatment device is 60mL h-1In 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-1In 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 3 h. The integral nitrogen-doped carbon aerogel 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.
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 side view photograph 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-1Under 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 (0-300min) ultraviolet-visible absorption spectrogram of the rhodamine B solution; FIG. 3(b) is a 3D printed monolithic nitrogen doped carbon aerogel and non-woven fabric3D printed real-time degradation rate curve of blocky nitrogen-doped carbon to RhB solution, wherein the curve 1 is that 3D printed integral nitrogen-doped carbon aerogel has the solution flow rate of 60mL h-1The 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-1Curve 3 is the flow rate of the bulk nitrogen-doped carbon for non-3D printing at a solution flow rate of 60mL h-1Curve 4 is the flow rate of the bulk nitrogen-doped carbon not printed in 3D at a solution flow rate of 120mL h-1The degradation rate curve of (2).
FIG. 4: in the bacterial liquid concentration of 106CFU mL-1PMS concentration of 1g L-1The flow rate is 60mL h-1Under 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 the bacterial liquid concentration of 107CFU mL-1PMS concentration of 1g L-1The flow rate is 120mL h-1Under 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. 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 microscope photographs of the 3D printed monolithic nitrogen-doped carbon aerogel material prepared in example 1 after the 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 intended to limit 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, 5 wt% (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 a 10mL disposable syringe tube, and an integral multi-stage porous structure model (cylinder shape, diameter multiplied by height: 1.9 cm. times.1.0 cm). Then, the established model is led into 3D printing software RepperHost in a DIW printer configuration computer, and the Slic3r embedded in the software is used for setting printing parameters: layer height (0.35mm, 22 gauge needle diameter. times.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 adding the syringe on 3D printing equipment. 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, 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 the sample at the temperature of-40 ℃ for 36 hours, and then pyrolyzing the sample for 1 hour at the temperature of 800 ℃ in a tubular furnace under the 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
The concentration of the RhB aqueous solution is 10ppm, the concentration of the PMS aqueous solution is 1g L-1Under the condition of (1), the total volume is 60mL h-1、120mL h-1The mixed solution of RhB and PMS (RhB and PMS were loaded in 2 separatory funnels, respectively, and were mixed together and flowed through the aerogel after the start of the reaction) was fed through the 3D-printed integrated nitrogen-doped carbon aerogel, and the reacted solution was drawn out at the same flow rate, and the uv-visible spectrum was measured on the drawn reaction solution at time intervals set as curves 1 and 2 in fig. 3 (b). The real-time efficiency of continuous degradation of flowing organic pollutants by 3D printing integral nitrogen-doped carbon aerogel activated PMS is evaluated by analyzing the change of the characteristic absorption peak area (lambda is 554nm at the characteristic absorption peak) of RhB in the reaction solution in an ultraviolet-visible absorption spectrum.
The degradation rate (D) is calculated by the formula:
D＝(A0-A)/A×100％
wherein D is the degradation rate of RhB at each set time point in the reaction, A0The 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, selecting escherichia coli as a research object, and researching the flow type sterilization performance of the 3D printing integral nitrogen-doped carbon aerogel through a colony forming experiment and a flat plate colony counting method. The concentration of the bacterial solution is 106The concentration of the CFU and PMS solution is 1g L-1The 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-1Under the condition, the flowing bacteria liquid is continuously treated by 3D printing the integral bionic nitrogen-doped carbon aerogel for 5min, 15min, 30min, 60min, 90min, 120min, 180min, 240min and 300min, 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.
Solubility in bacteria of 107The concentration of the CFU and PMS solution is 1g L-1The 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-1Under 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 a micron-scale pore structure formed by freeze-drying the extruded hydrogel precursor, wherein the average size of the pore structure is 15-80 nm (figure 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, the PMS solution concentration was 1g L-1The flow rate of the mixed solution is 60mL h-1The absorbance of RhB solution flowing through the 3D printed monolithic nitrogen-doped carbon aerogel for 5min rapidly decreased at the characteristic absorption peak (figure)3 (a)). According to the degradation rate calculation formula, the 3D printed monolithic nitrogen-doped carbon aerogel can achieve 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-1Under the condition (1), 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). The 3D printed monolithic nitrogen-doped carbon aerogel prepared in example 1 was shown to have 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 extracted 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-1Under the condition (1), the degradation rate of RhB within the first 5min is 77.6%. And (3) continuing the reaction, the nitrogen-doped carbon which is not printed by the 3D printing is washed away by water flow, the filter membrane at the bottom end of the injector is gradually blocked, finally the reaction solution is difficult to be pumped out by the micro peristaltic pump after 60min, and the degradation rate of RhB is greatly reduced to 62.7% (curve 3 in FIG. 3). At a solution flow rate of 120mL h-1Under 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, after the bacterial solution coating culture without the 3D printing monolithic nitrogen-doped carbon aerogel, almost all colonies were observed on the culture medium (fig. 4(j)), and after the bacterial solution coating culture for 5-300 min after the 3D printing monolithic nitrogen-doped carbon aerogel, no colony growth was observed on the culture medium (fig. 4(a) to fig. 4 (i)).
As shown in fig. 5, after the bacterial solution coating culture without the 3D printing monolithic nitrogen-doped carbon aerogel, almost all colonies on the culture medium were observed (fig. 5(f)), and after the bacterial solution coating culture with the 3D printing monolithic nitrogen-doped carbon aerogel for 5-180 min, no colony growth on the culture medium was observed (fig. 5(a) to fig. 5 (e)).
As shown in fig. 6, after the 3D printing integral nitrogen-doped carbon aerogel prepared in example 1 undergoes the RhB reaction, the millimeter-scale macroscopic appearance of the aerogel is substantially unchanged, and further amplification of the aerogel can observe that the microscopic micro-nano porous structure of the aerogel is also maintained relatively perfect.
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 × 1cm), 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 1 mm.
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. times.0.85), number of layers (15), fill (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-shaped pore diameter of about 1 mm.
Example 4
The procedure was as in example 1 except that:
1) the addition amount of HPMC in step 1) of example 1 was 4 wt%;
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: and 5%, preparing the prepared cylindrical 3D printing integral nitrogen-doped carbon aerogel, wherein the macroscopic latticed pore diameter is about 0.9 mm.
Claims (10)
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 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 a rotating speed of 500-800 rpm during the period, and heating the reaction system to 60-90 ℃ after the carbon source is added; after the raw materials are completely dissolved, slowly adding a rheological regulator with the dosage of 2-15 wt% of deionized water, after the raw materials are completely dissolved, closing heating, 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, then importing the established model into 3D printing software in a configuration computer of Direct Ink Writing (DIW) printing equipment, and setting appropriate printing parameters: the layer height is equal to the diameter of the needle head multiplied by 0.6-0.9, the layer number is equal to 3-30, the filling degree is equal to 15% -40%, and the speed is equal to 2-15 mm/s;
3) placing the nitrogen-doped carbon hydrogel precursor cooled to room temperature obtained in the step 1) into a disposable injector needle cylinder, centrifuging for 2-10 min to remove bubbles, connecting the needle cylinder with a 18, 20, 22 or 25-gauge printing needle head, and adding the needle cylinder 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;
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 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; finally, the printed sample was dried overnight to yield a 3D printed monolithic nitrogen-doped carbon aerogel having 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 salt sacrificial template in the step 1) is one of sodium chloride and sodium nitrate.
3. The method for preparing the 3D printing integral nitrogen-doped carbon aerogel with the self-supporting multi-stage porous structure according to claim 1, wherein the method comprises the following steps: the nitrogen source in the step 1) is one of urea and melamine.
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 natural carbon source material in the step 1) is one of agarose, pectin, gelatin, chitosan, sodium alginate and cellulose derivatives.
5. The method for preparing the 3D printing integral nitrogen-doped carbon aerogel with the self-supporting multi-stage porous structure according to claim 1, wherein the method comprises the following steps: the rheological regulator in the step 1) is one of hydroxypropyl methylcellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane and nano clay.
6. The method for preparing the 3D printing integral nitrogen-doped carbon aerogel with the self-supporting multi-stage porous structure according to claim 1, wherein the method comprises the following steps: 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.
7. 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.
8. 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.
9. 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 method of any one of claims 1 to 8.
10. Use of a 3D printed monolithic nitrogen doped carbon aerogel with a self-supportable multi-stage porous structure according to claim 9 for sewage purification.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210561326.6A CN114733453B (en) | 2022-05-23 | 2022-05-23 | Monolithic nitrogen-doped carbon catalytic material with multi-stage porous structure, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210561326.6A CN114733453B (en) | 2022-05-23 | 2022-05-23 | Monolithic nitrogen-doped carbon catalytic material with multi-stage porous structure, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114733453A true CN114733453A (en) | 2022-07-12 |
| CN114733453B CN114733453B (en) | 2023-04-11 |
Family
ID=82287062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210561326.6A Active CN114733453B (en) | 2022-05-23 | 2022-05-23 | Monolithic nitrogen-doped carbon catalytic material with multi-stage porous structure, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114733453B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180345598A1 (en) * | 2017-06-05 | 2018-12-06 | Lawrence Livermore National Security, Llc | System and method for forming activated carbon aerogels and performing 3d printing |
| CN109160800A (en) * | 2018-10-08 | 2019-01-08 | 吉林大学 | A method of monoblock type molecular sieve block is prepared based on 3D printing technique |
| CN110240484A (en) * | 2019-06-18 | 2019-09-17 | 西北工业大学 | A kind of method of 3D printing high-specific surface area high efficiency catalysts-support system |
| WO2019183461A1 (en) * | 2018-03-23 | 2019-09-26 | Lawrence Livermore National Security, Llc | Base-catalyzed sol-gel inks for direct ink writing of high resolution hierarchically porous carbon aerogels |
| CN113457649A (en) * | 2021-06-11 | 2021-10-01 | 上海簇睿低碳能源技术有限公司 | Integral boron-doped TS-1 catalyst carrier and preparation and application thereof |
| CN114195136A (en) * | 2022-01-05 | 2022-03-18 | 郑州大学 | Preparation method and application of 3D printing nitrogen-doped high-pyrrole graphene aerogel |
-
2022
- 2022-05-23 CN CN202210561326.6A patent/CN114733453B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180345598A1 (en) * | 2017-06-05 | 2018-12-06 | Lawrence Livermore National Security, Llc | System and method for forming activated carbon aerogels and performing 3d printing |
| WO2019183461A1 (en) * | 2018-03-23 | 2019-09-26 | Lawrence Livermore National Security, Llc | Base-catalyzed sol-gel inks for direct ink writing of high resolution hierarchically porous carbon aerogels |
| CN109160800A (en) * | 2018-10-08 | 2019-01-08 | 吉林大学 | A method of monoblock type molecular sieve block is prepared based on 3D printing technique |
| CN110240484A (en) * | 2019-06-18 | 2019-09-17 | 西北工业大学 | A kind of method of 3D printing high-specific surface area high efficiency catalysts-support system |
| CN113457649A (en) * | 2021-06-11 | 2021-10-01 | 上海簇睿低碳能源技术有限公司 | Integral boron-doped TS-1 catalyst carrier and preparation and application thereof |
| CN114195136A (en) * | 2022-01-05 | 2022-03-18 | 郑州大学 | Preparation method and application of 3D printing nitrogen-doped high-pyrrole graphene aerogel |
Non-Patent Citations (1)
| Title |
|---|
| 刘振星: "基于3d打印制备整体式炭材料及其吸附性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114733453B (en) | 2023-04-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Dong et al. | Cellulose/carbon composites and their applications in water treatment–a review | |
| Cheng et al. | Multifaceted applications of cellulosic porous materials in environment, energy, and health | |
| Zhang et al. | Corn stover–derived biochar for efficient adsorption of oxytetracycline from wastewater | |
| Inonu et al. | An emerging family of hybrid nanomaterials: metal–organic framework/aerogel composites | |
| Rana et al. | Water desalination using nanocelluloses/cellulose derivatives based membranes for sustainable future | |
| Halake et al. | Recent application developments of water-soluble synthetic polymers | |
| Zhang et al. | Advances in cellulose-metal organic framework composites: preparation and applications | |
| CN109516457A (en) | A kind of chitosan-based porous carbon ball and preparation method thereof | |
| Ma et al. | Shaping of metal-organic frameworks, a critical step toward industrial applications | |
| Tsang et al. | Recent development and applications of advanced materials via direct ink writing | |
| CN105000542A (en) | Preparation method for graphene-carbon nano tube three-dimensional structure composite material | |
| CN109925891B (en) | Small-aperture high-flux carbon nanotube low-pressure membrane and preparation method thereof | |
| CN110773006B (en) | Preparation method of hydrogel antibacterial filtering membrane containing copper oxide/cuprous oxide/carbon nano tube | |
| He et al. | Incorporating metal–organic frameworks into substrates for environmental applications | |
| CN1765770A (en) | Degradation controllable cellulose base microbe carrier stuffing for water disposal and its preparation method | |
| Ponce et al. | Recyclable photocatalytic composites based on natural hydrogels for dye degradation in wastewaters | |
| CN114733453B (en) | Monolithic nitrogen-doped carbon catalytic material with multi-stage porous structure, preparation method and application thereof | |
| Xia et al. | A review on pollutants remediation competence of nanocomposites on contaminated water | |
| CN109092260B (en) | Petroleum adsorption degradation material and preparation method thereof | |
| Liu et al. | Additively Manufacturing Metal− Organic Frameworks and Derivatives: Methods, Functional Objects, and Applications | |
| Roostaei et al. | Recent advances and progress in biotemplate catalysts for electrochemical energy storage and conversion | |
| CN104437439B (en) | A kind of amorphous nano-copper sulfide composite, preparation method and application | |
| CN104258852B (en) | The multi-layer porous photocatalysis film of titanium dioxide of modified by silver, Its Preparation Method And Use | |
| CN109433122A (en) | A kind of preparation method of inorganic/organic core shell structure capsule and obtained capsule | |
| CN100496709C (en) | A multi-channel titania photocatalysis membrane and method for making same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |