CN115304037A - 一种珊瑚状多孔氮化碳管的制备方法及应用 - Google Patents
一种珊瑚状多孔氮化碳管的制备方法及应用 Download PDFInfo
- Publication number
- CN115304037A CN115304037A CN202210770016.5A CN202210770016A CN115304037A CN 115304037 A CN115304037 A CN 115304037A CN 202210770016 A CN202210770016 A CN 202210770016A CN 115304037 A CN115304037 A CN 115304037A
- Authority
- CN
- China
- Prior art keywords
- carbon nitride
- tube
- preparation
- mixture
- porous
- 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
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 13
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 10
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims abstract description 8
- 229940048086 sodium pyrophosphate Drugs 0.000 claims abstract description 8
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims abstract description 8
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims abstract description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004202 carbamide Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000002071 nanotube Substances 0.000 claims description 32
- 230000001699 photocatalysis Effects 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 230000015556 catabolic process Effects 0.000 claims description 10
- 238000006731 degradation reaction Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 230000001954 sterilising effect Effects 0.000 claims description 3
- 238000004659 sterilization and disinfection Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 239000011941 photocatalyst Substances 0.000 abstract description 7
- 241000894006 Bacteria Species 0.000 abstract description 5
- 230000006798 recombination Effects 0.000 abstract description 3
- 238000005215 recombination Methods 0.000 abstract description 3
- 239000003242 anti bacterial agent Substances 0.000 abstract description 2
- 229940088710 antibiotic agent Drugs 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 10
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 229960004989 tetracycline hydrochloride Drugs 0.000 description 10
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 9
- 241000191967 Staphylococcus aureus Species 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000003115 biocidal effect Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000002779 inactivation Effects 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000002953 phosphate buffered saline Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000014653 Carica parviflora Nutrition 0.000 description 1
- 241000243321 Cnidaria Species 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000006142 Luria-Bertani Agar Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241000607142 Salmonella Species 0.000 description 1
- 239000004098 Tetracycline Substances 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- LUFPJJNWMYZRQE-UHFFFAOYSA-N benzylsulfanylmethylbenzene Chemical compound C=1C=CC=CC=1CSCC1=CC=CC=C1 LUFPJJNWMYZRQE-UHFFFAOYSA-N 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001332 colony forming effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 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
- 230000020477 pH reduction Effects 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229960002180 tetracycline Drugs 0.000 description 1
- 229930101283 tetracycline Natural products 0.000 description 1
- 235000019364 tetracycline Nutrition 0.000 description 1
- 150000003522 tetracyclines Chemical class 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0605—Binary compounds of nitrogen with carbon
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/13—Nanotubes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- 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)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Plant Pathology (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Nanotechnology (AREA)
- General Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Agronomy & Crop Science (AREA)
- Toxicology (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种珊瑚状多孔氮化碳管的制备方法及应用。制备过程包括:水热三聚氰胺和焦磷酸钠制备超分子前躯体,将前躯体置于管式炉内高温煅烧得到氮化碳微管,再将氮化碳微管与尿素混合放入马弗炉二次煅烧,得到一种多孔珊瑚状结构g‑C3N4管中管。本发明方法安全、无毒的制备了形貌新颖且具有高效可见光驱动的珊瑚状多孔g‑C3N4管,得到的光催化剂超越了简单的空心氮化碳管,提高了可见光利用率、减小了光生电子空穴复合率,能在可见光照射下高效率灭活水中细菌及去除水体中的抗生素。
Description
技术领域
本发明属于纳米氮化碳材料领域,涉及一种珊瑚状多孔氮化碳管(g-C3N4)的制备方法及应用,即g-C3N4管中管的制备方法及应用,尤其是其作为光催化剂材料的应用。
背景技术
随着工业化经济的快速发展,水污染问题及其危害越来越受到人们的关注。在饮用水中病原体能够快速快速的进行传播,导致人类出现严重疾病甚至死亡。盐酸四环素作为一种广谱抗菌剂,已广泛用于治疗革兰氏阳性菌和革兰氏阴性菌引起的感染,特别是在农业、水产养殖和畜牧业中。由于盐酸四环素的自然降解性和生物降解性较差,抗生素污染可长期滞留在水系统中,诱导产生耐药菌。因此,获得一种快速有效的去除水中抗生素和微生物污染的方法是当务之急。目前已探索了大量方法来解决抗生素残留问题:吸附法、光催化法、生物降解法、高级氧化法等(Environ Manage,2020.260:p.110125)。在这些方法中,光催化技术以其绿色、高效、经济、环保的特点受到了科学家们的广泛关注。利用光催化剂消除有机污染物、灭活有害细菌和产生清洁能源成为近几十年来最热门的话题之一。然而,这些光催化剂存在两个关键缺陷:生产成本过高和光催性能差。
氮化碳(g-C3N4)是一种带隙较窄(2.7eV)的非金属半导体材料,其主要由碳元素和氮元素构成,具有类石墨层状结构(International Journal of Hydrogen Energy,2020.45(1):p.337-379.)。氮化碳具有可见光响应性好、化学稳定性好、易于合成、拥有较强的氧化还原能力等突出特点。不幸的是,用氰胺前驱体直接热聚合法制备的氮化碳的光催化效率还远远不能令人满意。这在很大程度上是由于氮化碳中光电生成的电子-空穴对的比表面积低和复合率高。为了克服这些限制,提高氮化碳的光催化活性,人们在化学结构调整和纳米结构设计方面做了大量工作,包括与共轭分子共聚(Journal of MaterialsChemistry A,2020.8(48):p.25626-25648)、形貌控制(Applied Catalysis B:Environmental,2017,209:p.161-173)、掺杂杂原子(Nano Research,2019.12(9):p.2385-2389)、以及与其他半导体的复合等。特别是纳米结构的设计既能增加比表面积,又能促进光载体的转移,从而显著提高了氮化碳的光催化活性。
然而现有一维氮化碳纳米管表面较为光滑,所提供的反应活性位点仍然不够多,导致其光催化降效率依然不够强。而且现有的氮化碳纳米管制备难度高,较难满足使用需求。
发明内容
本发明的目的在于解决现有一维氮化碳纳米管光催化效率低及难制备的问题,提供了一种安全简单的珊瑚状多孔氮化碳纳米管、其制备方法及其在光催化中的应用。该方法利用三聚氰胺、尿素等材料进行水热、煅烧,得到珊瑚状多孔g-C3N4管中管,该制备过程简单、快捷并便于操作,制备得到的光催化剂具有较好的可见光催化效率,对于金葡球菌的灭活以及抗生素盐酸四环素的光催化降解有明显的效果。本发明的技术方案如下:
本发明一方面提供了一种珊瑚状多孔氮化碳管的制备方法,包括以下步骤:
1)将三聚氰胺溶解在去离子水中;将其在70~85℃下强烈搅拌30分钟,然后加入焦磷酸钠搅拌;待溶液澄清后,将溶液置于高压反应釜中,在180℃下加热8~10h;结束后,将混合物离心,洗涤,干燥。,得到氮化碳前驱体;
2)取步骤1制备得到的氮化碳前躯体放入管式炉中,在氮气氛围保护下在500℃下保温2~4h;然后自然冷却到室温,再研磨成粉末,制备得到普通氮化碳纳米管;
3)取步骤2制备得到的普通氮化碳纳米管与尿素混合,置于马弗炉中在520~550℃下煅烧,升温速率为5℃/min,保温1小时;之后自然冷却到室温后取出研磨,制备得到了珊瑚状所述多孔氮化碳管。
在一些具体的实施方式中,在步骤1)中,当三聚氰胺为1g时,所用的用于溶解的去离子水可以是100~200ml,此时的搅拌温度可以是85℃。用于保持搅拌温度的方法可以是水浴;干燥具体可以是60℃下干燥12h。
作为优选,步骤1中,所述三聚氰胺与焦磷酸钠摩尔比为1:1-1.5。
作为优选,步骤1中,所述洗涤具体为去离子水冲洗次数为3~5次,无水乙醇冲洗次数为3~5次。
作为优选,步骤2中,管式炉升温速率为2.0~2.5℃/min,保温时间为4h。
作为优选,步骤3中,所述普通氮化碳纳米管与尿素的质量比为1:1-1.5。作为优选,步骤1中所述三聚氰胺溶解在去离子水中的浓度为0.005-0.01g/ml,优选0.01g/ml。
作为优选,步骤1中所述搅拌的温度为85℃;所述高压反应釜的加热时间为10h。
作为优选,步骤2中所述氮气气压为0.1MPa,流速为50ml/min。
本发明另一方面还提供了一种上述方法制备得到的珊瑚状多孔氮化碳管。
本发明另一方面还提供了一种上述珊瑚状多孔氮化碳管的光催化用途,所述光催化用途指在可见光下催化灭菌或催化有机物降解。更为具体的是,所述的菌为金葡球菌;所述的有机物为四环素。
有技术相比,本发明的有益效果是:本发明制备方法简单、经济便捷,制备的光催化剂具有优良的可见光催化性能,在可见光照射下能够高效的灭活金葡球菌以及降解盐酸四环素,分别是纯的氮化碳纳米管的4倍和1.5倍。
本发明所制备的管中管结构的氮化碳管通过自组装成功地获得了多孔珊瑚状结构。通过纳米管的结构作用机制,有效增强了半导体材料的光催化性能。增大的比表面积为氧化还原反应提供了丰富的活性位点,管状径向形成的光反射和折射提高了光的吸收和利用,薄壳横向加快了电荷载流子的短距离传输,同时多孔的珊瑚结构提供更多的接触位点。因此制备出高效可见光催化剂新材料,从而为实现治理水中污染物,金葡球菌的灭活以及抗生素的降解具有很重要的意义。
附图说明
图1为对比例1制备得到的氮化碳纳米管扫描电镜图,;
图2为实施例1制备得到的珊瑚状多孔g-C3N4管中管可见光催化剂横截面的扫描电镜图;
图3为实施例1制备得到的珊瑚状多孔g-C3N4管中管的透射电镜图;
图4为实施例1制备得到的珊瑚状多孔g-C3N4管中管和对比例1制备得到的氮化碳纳米管的XRD图;
图5为实施例1制备得到的珊瑚状多孔g-C3N4管中管和对比例1制备得到的氮化碳纳米管在可见光照射下光催化灭活金葡球菌性能图;
图6为实施例1制备得到的珊瑚状多孔g-C3N4管中管和对比例1制备得到的氮化碳纳米管在可见光照射下光催化降解盐酸四环素降解性能图。
具体实施方式
以下将通过实施例来详细说明本申请的实施方式,借此对本申请如何应用技术手段来解决技术问题并达成技术功效的实现过程能充分理解并据以实施。
本申请中所用原料、设备,若无特别说明,均为本领域的常用原料、设备,均来自市售产品。本申请中所用方法,若无特别说明,均为本领域的常规方法。
本申请还存在其它多种可实施的技术方案,在此不做一一列举,本申请权利要求中要求保护的技术方案都是可以实施的。
“包含”或“包括”旨在表示组合物(例如介质)和方法包括所列举的要素,但不排除其他要素。当用于定义组合物和方法时,“基本上由……组成”意味着排除对于所述目的的组合具有任何重要意义的其他要素。因此,基本上由本文定义的元素组成的组合物不排除不会实质上影响要求保护的本申请的基本和新颖特征的其他材料或步骤。“由……组成”是指排除其他组成部分的微量元素和实质性的方法步骤。由这些过渡术语中的每一个定义的实施方案都在本申请的范围内。
实施例1:
1)将1g三聚氰胺溶解在100ml的去离子水中。将其放到85℃的水浴锅中,并强烈搅拌30分钟后将焦磷酸钠按摩尔比1:1加入到溶液中。待溶液澄清后,混合物倒进内衬中,放到高压反应釜中,在180℃下加热10h。待反应釜自然冷却后,将混合物去离子水冲洗次数为3次,无水乙醇冲洗次数为3次,并在60℃下干燥12h。
2)取步骤1制备得到的氮化碳前躯体放入氧化铝坩埚中,在管式炉中通过氮气氛围保护下以2.5℃/min的加热速率在500℃下加热4h,氮气气压为0.1MPa,流速为50ml/min。煅烧结束后自然冷却到室温,将得到的样品研磨成粉末,制备得到了普通氮化碳纳米管;
3)取步骤2制备得到的氮化碳纳米管与尿素进行质量比1:1.5混合,放入带盖子的坩埚内,盖上盖子,留出缝隙,放置于马弗炉中在550℃下煅烧,升温速率为5℃/min,保温1小时。随马弗炉自然冷却到室温后取出研磨,制备得到了珊瑚状多孔g-C3N4管中管。实施例2:与实施例1不同的是步骤1中用于溶解的去离子水为150ml。其他与实施例1相同。实施例3:与实施例1不同的是步骤1中三聚氰胺与焦磷酸钠按摩尔比1:1.5。其他与实施例1相同。
实施例4:与实施例1不同的是步骤2中管式炉加热速率为2℃/min。其他与实施例1相同。
实施例5:与实施例1不同的是步骤2中管式炉保温时间为2h。其他与实施例1相同。实施例2-4所制备得到的多孔氮化碳管形貌与实施例1类似。对比例1:
1)将1g三聚氰胺溶解在100ml的去离子水中。将其放到85℃的水浴锅中,并强烈搅拌30分钟后将焦磷酸钠按摩尔比1:1加入到溶液中。待溶液澄清后,混合物倒进内衬中,放到高压反应釜中,在180℃下加热10h。待反应釜自然冷却后,将混合物去离子水冲洗次数为3次,无水乙醇冲洗次数为3次,并在60℃下干燥12h,即得到氮化碳前驱体。
2)取步骤1制备得到的氮化碳前躯体放入氧化铝坩埚中,在管式炉中通过氮气氛围保护下以2.0~2.5℃/min的加热速率在500℃下加热2~4h,氮气气压为0.1MPa,流速为50ml/min。煅烧结束后自然冷却到室温,将得到的样品研磨成粉末,制备得到了普通氮化碳纳米管。
即实施例1中步骤1和2制备得到的普通氮化碳纳米管。普通氮化碳微管(如图1),管内为空心结构,管壁光滑,比表面积为24m2·g-1。
对比例2:
中国专利,CN110002414 A(一种多孔氮化碳纳米管的制备方法),该方法以富氮有机物为原料,经磷酸酸化水热处理后得到超分子前驱体,洗涤干燥后置于马弗炉内煅烧得到多孔氮化碳纳米管。然而该方法在制备多孔氮化碳纳米管过程中需要使用多种原料和强酸溶剂,并且马弗炉一次煅烧无法烧出具有类似于珊瑚装的多孔(管中管)结构,限制了光催化性能的进一步提高和多种应用。
对比例3:
中国专利,CN108383091A(一种S、P掺杂的g-C3N4管中管及其制备方法),该方法通过掺杂将三聚氰胺、磷酸二氢铵和二苄基硫醚混合,得到均匀的混合物。将该混合物至550-700℃进行煅烧,所得产物具有S、P掺杂的g-C3N4管中管结构。该方法虽然能制备得到氮化碳管中管,但形貌难以调控,管壁无多孔,掺杂过程中使用有毒易燃的有机试剂,不利于环境安全。此外,无具体光催化方面的实际应用。
本发明使用以下实施例验证珊瑚状多孔g-C3N4管中管光催化剂具有提高的可见光效率:
实施例1对比例1得到的普通氮化碳纳米管扫描电镜图如图1所示,从图中可以看到形貌规整的六边形纳米管,管口直径为1μm,管壁光滑,管内中空;
通过本实施例1制备的珊瑚状多孔g-C3N4管中管可见光催化剂横截面的扫描电镜图如图2所示,由图可以观察到管长为5-10μm,直径为7μm。六边形纳米管壁的厚度为500nm,管内有许多清晰可见的珊瑚状小孔,孔径尺寸约为20nm,形成独特的管中管结构;
通过本实施例1制备的珊瑚状多孔g-C3N4管中管的透射电镜图如图3所示,从图3中可以看到明显的孔隙,说明了多孔的存在,且整体形貌规整,为管状的结构;
通过本实施例1制备的多孔氮化碳纳米管和普通氮化碳纳米管的XRD图如图4所示,可以观察到二者的XRD谱图相似。前一个峰位于13.3°,对应的是三s-三嗪单元的面内结构堆积((100)晶面,而27.5°的峰则是共轭芳香体系((002)晶面的面内堆积。多孔氮化碳纳米管发生轻微偏移,宽度变小,表明晶体结晶度高,晶面生长规律。
为了验证实施例1得到的珊瑚状多孔g-C3N4管中管作为光催化材料的活性,进行了以下测试。
测试例1::可见光灭菌催化活性
配置菌悬浮液,金葡球菌悬液用磷酸盐缓冲液(PBS,0.01M,pH 7.4)稀释,得到每毫升约107个克隆形成单位(CFU/mL)的细胞计数。通过使用带有420nm截止滤光片的300W氙灯作为光源,使用超级恒温水浴使反应体系的温度控制在20℃。将20ml的金葡球菌悬浮液和10mg的催化剂粉末放入50ml的烧杯中。将混合物在黑暗中保持0.5h以达到均匀分散。在光照时间60min下,每间隔20分钟收集沙门氏菌液500μl,并用PBS稀释。将100μl的受试悬浮液涂抹在新鲜制备的LB琼脂平板上,37℃孵育24h后计数菌落数以确定存活菌落。
通过本实施例1制备的珊瑚状多孔g-C3N4管中管的可见光催化灭活金葡球菌溶液随时间变化的降解效果如图5所示,从图中可见多孔氮化碳纳米管具有良好的可见光催化性能,在60min内能完全灭活6log cfu/ml的金葡球菌,相比普通氮化碳纳米管降解效果提高了4倍。
测试例2::可见光催化活性
取质量为20mg实施例1得到的珊瑚状多孔g-C3N4管中管放置于150ml烧杯中,再加入100ml的浓度为20mg/L的盐酸四环素溶液,于不断的磁力搅拌下置于300W氙灯下照射,氙灯上覆盖了一个420nm的滤光片滤去紫外光,每间隔10min快速取出5ml盐酸四环素并通过紫外分光光度计测量盐酸四环素的吸光度变化,测量完后倒回继续反应;
通过本实施例制备的珊瑚状多孔g-C3N4管中管的可见光催化降解盐酸四环素溶液随时间变化的降解效果如图6所示,从图中可见珊瑚状多孔g-C3N4管中管具有良好的可见光催化性能,对盐酸四环素溶液在60min内的降解达到了72%,相比氮化碳纳米管降解效果提高了1.5倍,这种效果主要是由于多孔珊瑚状的管中管结构更有利于光生电子空穴的迁移及有效分离,提供更多的催化活性位点。
本申请说明书中未作详细描述的内容属于本领域技术人员的公知常识。
如在通篇说明书及权利要求当中所提及的“包含”为一开放式用语,故应解释成“包含但不限定于”。“大致”是指在可接收的误差范围内,本领域技术人员能够在一定误差范围内解决所述技术问题,基本达到所述技术效果。
还需要说明的是,术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含,从而使得包括一系列要素的商品或者系统不仅包括那些要素,而且还包括没有明确列出的其他要素,或者是还包括为这种商品或者系统所固有的要素。在没有更多限制的情况下,由语句“包括一个……”限定的要素,并不排除在包括所述要素的商品或者系统中还存在另外的相同要素。
上述说明示出并描述了本申请的若干优选实施例,但如前所述,应当理解本申请并非局限于本文所披露的形式,不应看作是对其他实施例的排除,而可用于各种其他组合、修改和环境,并能够在本文所述发明构想范围内,通过上述教导或相关领域的技术或知识进行改动。而本领域人员所进行的改动和变化不脱离本申请的精神和范围,则都应在本申请所附权利要求的保护范围。
Claims (10)
1.一种珊瑚状多孔氮化碳管的制备方法,其特征在于,包括以下步骤:
1)将三聚氰胺溶解在去离子水中;将其在70~85℃下强烈搅拌30分钟,然后加入焦磷酸钠搅拌;待溶液澄清后,将溶液置于高压反应釜中,在180℃下加热8~10h;结束后,将混合物离心,洗涤,干燥,得到氮化碳前驱体;
2)取步骤1制备得到的氮化碳前躯体放入管式炉中,在氮气氛围保护下在500℃下保温2~4h;然后自然冷却到室温,再研磨成粉末,制备得到普通氮化碳纳米管;
3)取步骤2制备得到的普通氮化碳纳米管与尿素混合,置于马弗炉中在520~550℃下煅烧,升温速率为5℃/min,保温1小时;之后自然冷却到室温后取出研磨,制备得到了珊瑚状所述多孔氮化碳管。
2.根据权利要求1所述的制备方法,其特征在于,步骤1中,所述三聚氰胺与焦磷酸钠摩尔比为1:1-1.5。
3.根据权利要求1所述的制备方法,其特征在于,步骤1中,所述洗涤具体为去离子水冲洗次数为3~5次,无水乙醇冲洗次数为3~5次。
4.根据权利要求1所述的制备方法,其特征在于,步骤2中,管式炉升温速率为2.0~2.5℃/min,保温时间为4h。
5.根据权利要求1所述的制备方法,其特征在于,步骤3中,所述普通氮化碳纳米管与尿素的质量比为1:1-1.5。
6.根据权利要求1所述的制备方法,其特征在于,步骤1中所述三聚氰胺溶解在去离子水中的浓度为0.005-0.01g/ml,优选0.01g/ml。
7.根据权利要求1所述的制备方法,其特征在于,步骤1中所述搅拌的温度为85℃;所述高压反应釜的加热时间为10h。
8.根据权利要求1所述的制备方法,其特征在于,步骤2中所述氮气气压为0.1MPa,流速为50ml/min。
9.一种根据权利要求1所述方法制备得到的珊瑚状多孔氮化碳管。
10.一种权利要求9所述珊瑚状多孔氮化碳管的光催化用途,所述光催化用途指在可见光下催化灭菌或催化有机物降解。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210770016.5A CN115304037B (zh) | 2022-07-01 | 2022-07-01 | 一种珊瑚状多孔氮化碳管的制备方法及应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210770016.5A CN115304037B (zh) | 2022-07-01 | 2022-07-01 | 一种珊瑚状多孔氮化碳管的制备方法及应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN115304037A true CN115304037A (zh) | 2022-11-08 |
CN115304037B CN115304037B (zh) | 2023-07-21 |
Family
ID=83855200
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210770016.5A Active CN115304037B (zh) | 2022-07-01 | 2022-07-01 | 一种珊瑚状多孔氮化碳管的制备方法及应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115304037B (zh) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108383091A (zh) * | 2017-12-28 | 2018-08-10 | 济南大学 | 一种S、P掺杂的g-C3N4管中管及其制备方法 |
-
2022
- 2022-07-01 CN CN202210770016.5A patent/CN115304037B/zh active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108383091A (zh) * | 2017-12-28 | 2018-08-10 | 济南大学 | 一种S、P掺杂的g-C3N4管中管及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN115304037B (zh) | 2023-07-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109603880B (zh) | 中空管状氮化碳光催化剂及其制备方法和应用 | |
CN108940338B (zh) | 钾元素掺杂多孔氮化碳光催化剂及其制备方法和应用 | |
Li et al. | Er-doped g-C3N4 for photodegradation of tetracycline and tylosin: high photocatalytic activity and low leaching toxicity | |
CN108940344B (zh) | 改性石墨相氮化碳光催化剂及其制备方法和应用 | |
Qayum et al. | Efficient decontamination of multi-component wastewater by hydrophilic electrospun PAN/AgBr/Ag fibrous membrane | |
CN109603882B (zh) | 利用改性碳量子点负载中空管状氮化碳光催化剂处理有机污染物和光催化杀菌的方法 | |
CN105289674A (zh) | 一种AgVO3/Ag3PO4异质结复合光催化剂及其制备方法和应用 | |
CN107297204A (zh) | 一种以活性炭纤维为载体的TiO2纳米棒光催化网的制备方法 | |
CN109317183B (zh) | 一种氮化硼量子点/超薄多孔氮化碳复合光催化材料及其制备方法和应用 | |
CN112619659B (zh) | 一种氧化镍纳米片和钼酸铋纳米纤维异质结光催化材料及其制备方法与应用 | |
Mehmood et al. | Immobilizing a visible light-responsive photocatalyst on a recyclable polymeric composite for floating and suspended applications in water treatment | |
CN112958061B (zh) | 一种氧空位促进直接Z机制介孔Cu2O/TiO2光催化剂及其制备方法 | |
CN108686658B (zh) | 一种C-QDs-Fe2O3/TiO2复合光催化剂及其制备方法 | |
Gao et al. | Bi-doped graphitic carbon nitride nanotubes boost the photocatalytic degradation of Rhodamine B | |
CN105435847A (zh) | 一种Bi2WO6/BiOI@季铵盐无机/有机复合光催化杀菌剂及其制备方法 | |
CN111744503A (zh) | 一种Z型异质结MoS2/Bi2WO6复合光催化剂及其制备方法和应用 | |
CN113244961B (zh) | 双金属CoCu-MOF可见光催化剂及其制备方法和应用 | |
CN113600164A (zh) | 一种铁掺杂碳量子点/石墨相氮化碳复合光催化剂的制备方法及应用 | |
CN105688948A (zh) | 一种光催化剂及其制备方法和应用 | |
CN111229313B (zh) | 一种花球状BiOCl/TCPP复合光催化剂的制备方法及其应用 | |
CN111686769A (zh) | 一种光催化剂及其制备方法和应用 | |
CN115304037B (zh) | 一种珊瑚状多孔氮化碳管的制备方法及应用 | |
CN113083281B (zh) | 一种钼酸铋/碳柔性膜光催化材料及其制备方法与应用 | |
CN108793312A (zh) | 利用氮化碳/氮掺中空介孔碳/三氧化二铋三元z型光催化剂催化去除抗生素的方法 | |
Wu et al. | Monolithic ceramic foams for ultrafast photocatalytic inactivation of bacteria |
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 |