CN115845893A - Method for in-situ construction of metal-doped two-dimensional carbon nitride nanosheet/carbon nanotube multilevel structure and product thereof - Google Patents
Method for in-situ construction of metal-doped two-dimensional carbon nitride nanosheet/carbon nanotube multilevel structure and product thereof Download PDFInfo
- Publication number
- CN115845893A CN115845893A CN202211257820.XA CN202211257820A CN115845893A CN 115845893 A CN115845893 A CN 115845893A CN 202211257820 A CN202211257820 A CN 202211257820A CN 115845893 A CN115845893 A CN 115845893A
- Authority
- CN
- China
- Prior art keywords
- carbon nitride
- salt
- doped
- nickel
- cobalt
- 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 122
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 99
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 99
- 239000002135 nanosheet Substances 0.000 title claims abstract description 96
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 12
- 238000010276 construction Methods 0.000 title description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 71
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000005530 etching Methods 0.000 claims abstract description 34
- 230000009467 reduction Effects 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 9
- 150000001868 cobalt Chemical class 0.000 claims abstract description 9
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000002815 nickel Chemical class 0.000 claims abstract description 9
- PVKCVCDTYNNNOG-UHFFFAOYSA-N 1,3,5-triazine-2,4,6-triamine;hydrobromide Chemical compound [Br-].NC1=NC(N)=[NH+]C(N)=N1 PVKCVCDTYNNNOG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims abstract description 4
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 26
- 239000001257 hydrogen Substances 0.000 claims description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims description 26
- 238000004321 preservation Methods 0.000 claims description 24
- 239000000919 ceramic Substances 0.000 claims description 20
- 238000005336 cracking Methods 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000011261 inert gas Substances 0.000 claims description 13
- 239000011812 mixed powder Substances 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000010453 quartz Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 9
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- 150000002505 iron Chemical class 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- SFOKDWPZOYRZFF-UHFFFAOYSA-H 2,3-dihydroxybutanedioate;iron(3+) Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O SFOKDWPZOYRZFF-UHFFFAOYSA-H 0.000 claims description 2
- ZEYKLMDPUOVUCR-UHFFFAOYSA-N 2-chloro-5-(trifluoromethyl)benzenesulfonyl chloride Chemical compound FC(F)(F)C1=CC=C(Cl)C(S(Cl)(=O)=O)=C1 ZEYKLMDPUOVUCR-UHFFFAOYSA-N 0.000 claims description 2
- XXSPKSHUSWQAIZ-UHFFFAOYSA-L 36026-88-7 Chemical compound [Ni+2].[O-]P=O.[O-]P=O XXSPKSHUSWQAIZ-UHFFFAOYSA-L 0.000 claims description 2
- 239000005955 Ferric phosphate Substances 0.000 claims description 2
- FRHBOQMZUOWXQL-UHFFFAOYSA-L ammonium ferric citrate Chemical compound [NH4+].[Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FRHBOQMZUOWXQL-UHFFFAOYSA-L 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000152 cobalt phosphate Inorganic materials 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 2
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 claims description 2
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 claims description 2
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 229960004642 ferric ammonium citrate Drugs 0.000 claims description 2
- 229940032958 ferric phosphate Drugs 0.000 claims description 2
- 229940032950 ferric sulfate Drugs 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 235000000011 iron ammonium citrate Nutrition 0.000 claims description 2
- 239000004313 iron ammonium citrate Substances 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- XHQSLVIGPHXVAK-UHFFFAOYSA-K iron(3+);octadecanoate Chemical compound [Fe+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XHQSLVIGPHXVAK-UHFFFAOYSA-K 0.000 claims description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- JMWUYEFBFUCSAK-UHFFFAOYSA-L nickel(2+);octadecanoate Chemical compound [Ni+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O JMWUYEFBFUCSAK-UHFFFAOYSA-L 0.000 claims description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000000843 powder Substances 0.000 abstract description 46
- 238000005516 engineering process Methods 0.000 abstract description 13
- 238000004523 catalytic cracking Methods 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 description 13
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 9
- 238000000227 grinding Methods 0.000 description 9
- 230000007480 spreading Effects 0.000 description 9
- 238000003892 spreading Methods 0.000 description 9
- 238000009210 therapy by ultrasound Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 230000001699 photocatalysis Effects 0.000 description 7
- 239000011941 photocatalyst Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- BKXAWQXZFFNQHY-UHFFFAOYSA-N C(C)O.[N+](=O)([O-])[O-].[Co+2].[N+](=O)([O-])[O-] Chemical compound C(C)O.[N+](=O)([O-])[O-].[Co+2].[N+](=O)([O-])[O-] BKXAWQXZFFNQHY-UHFFFAOYSA-N 0.000 description 1
- 238000003775 Density Functional Theory Methods 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Images
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a method for preparing a metal-doped two-dimensional carbon nitride nanosheet/carbon nanotube multilevel structure by utilizing a catalytic cracking technology and a product thereof. Firstly, obtaining bulk-phase carbon nitride by heat treatment of one or more of melamine, melamine hydrobromide, cage-shaped phosphate melamine salt and melamine cyanurate, continuously carrying out hot etching on the synthesized powder for two times to obtain two-dimensional carbon nitride nanosheets, uniformly mixing the nanosheets with water or ethanol solution of ferric salt, nickel salt or cobalt salt with a certain concentration, drying the nanosheets, and then placing the nanosheets in an atmosphere furnace for reduction and catalytic cracking to obtain the metal-doped two-dimensional carbon nitride nanosheets/carbon nano tube multilevel structure. Different from the common composite material of carbon nitride and carbon nano tubes which are mechanically mixed, the metal-doped carbon nitride nano sheet/carbon nano tube obtained by the method has obvious multistage structural characteristics, namely, the highly-oriented one-dimensional carbon nano tube is generated on the surface of the metal-doped two-dimensional carbon nitride nano sheet in situ.
Description
Technical Field
The invention belongs to the technical field of inorganic material preparation, and particularly relates to a method for constructing a metal-doped two-dimensional carbon nitride nanosheet/carbon nanotube multilevel structure in situ and a product thereof.
Background
Energy is the basic power for social and economic operation and development, but the industrial and social development of the past hundred years consumes a large amount of non-renewable fossil fuels such as coal, petroleum and natural gas, and discharges a large amount of greenhouse gases and toxic gases such as carbon dioxide, sulfur dioxide and nitric oxide, so that the energy is increasingly exhausted and the environment is continuously worsened, and the human beings face serious survival challenges. Solar energy is a natural energy with abundant reserves, green and renewable, and the research and development of technical means for efficiently utilizing the solar energy is one of the main directions of energy development of human beings at present. The semiconductor photocatalysis technology drives a series of important chemical reactions through sunlight, can convert low-density and dispersed solar energy into high-density and high-concentration chemical energy or directly degrade organic pollutants, and is widely concerned by researchers at home and abroad. Among them, the key to the photocatalytic technology is the development of a catalytic material with high activity, high stability and low cost.
The polymer semiconductor carbon nitride has moderate band gap, high thermal stability and chemical stability, abundant and cheap raw materials and simple preparation process, and particularly has great application value in the fields of photocatalytic degradation of organic pollutants and hydrogen production by water photolysis. Carbon nitride has a layered structure similar to graphite with an interlayer spacing of about 0.326nm, slightly less than that of graphite (0.335 nm). In the structure of the carbon nitride, both carbon atoms and nitrogen atoms in the layer are sp 2 Hybridization and alternate arrangement, the hexagonal aromatic structure similar to a benzene ring is formed by sigma bond connection, the rings are connected through nitrogen atoms at the tail section to form an infinitely expanded plane, and the layers are connected by Van der Waals force. The Wangxing morning of Fuzhou university firstly discovers that the metal-free carbon nitride is under the condition of visible lightRealize decomposition of H 2 O to H 2 And through the density functional theory and the electrochemical method, the band gap structure research of the carbon nitride shows that the band gap between the highest occupied orbit and the lowest unoccupied orbit is about 2.7eV, and the semiconductor band gap has a typical semiconductor band structure. More importantly, the carbon nitride has proper valence band and conduction band positions to satisfy H 2 Decomposition of O into H 2 And O 2 The thermodynamic requirements of (1) < Nature Materials, 2009, 8 (1): 76-80.). Since then, the new non-metallic photocatalytic material has been greatly valued and studied, and is considered to be the most potential photocatalytic material.
However, as a photocatalyst, carbon nitride has some problems, such as small specific surface area, high recombination rate of photogenerated carriers, low quantum efficiency, large forbidden band width, and the like, and has a large distance from the aspect of large-scale and efficient solar energy utilization for water pollution treatment or hydrogen production by photolysis of water, because only a small amount of visible light can be utilized. In order to make up for the inherent defects of a single photocatalyst, the carbon nitride-based composite material is a simple and effective method, the separation of photo-generated electrons and holes can be accelerated, the service life of photo-generated carriers can be prolonged, the photoelectric conversion efficiency is improved, and the spectrum absorption range is expanded.
The existing research shows that the carbon nitride nanosheet-carbon nanotube composite material has excellent photocatalytic characteristics, in the photocatalytic process, the carbon nanotube can assist in enhancing the visible light absorption of a semiconductor photocatalyst, can also effectively promote the separation and transfer of a photon-generated carrier, and the abundant modification method on the surface enables the carbon nitride nanosheet-carbon nanotube composite material to play the role of an active center in a plurality of catalytic reactions. Carbon nitride nanosheet/carbon nanotube composite materials (Angewandte Chemie, 2014, 126 (28): 7409-7413.) are synthesized by Joule jade article and the like of the university of Adeland through electrostatic adsorption and a pi-pi stacking strategy, but the carbon nanotubes synthesized by the method are scattered on the surface of the carbon nitride nanosheets and are not firmly combined, and the density of the carbon nanotubes on the surface of the carbon nitride nanosheets cannot be regulated. Therefore, it is a difficult problem how to in-situ directionally synthesize carbon nanotubes with controllable density on two-dimensional carbon nitride nano-sheets.
Disclosure of Invention
The invention aims to provide a method for constructing a metal-doped two-dimensional carbon nitride nanosheet/carbon nanotube multilevel structure in situ with stable performance, convenient operation and low cost and a product thereof.
In order to solve the technical problems, the technical scheme of the invention is as follows: a method for constructing a metal-doped two-dimensional carbon nitride nanosheet/carbon nanotube multilevel structure in situ is characterized by comprising the following steps:
the method comprises the following steps: putting one or more of melamine, melamine hydrobromide, cage-shaped phosphate melamine salt and melamine cyanurate into a ceramic or quartz crucible, and carrying out heat treatment to obtain bulk-phase carbon nitride;
step two: thermally etching the bulk carbon nitride prepared in the step one twice to obtain two-dimensional carbon nitride nanosheets;
step three: uniformly mixing the two-dimensional carbon nitride nanosheets prepared in the step two with iron salt, nickel salt and cobalt salt aqueous solution or ethanol solution with certain concentration, and drying to obtain mixed powder;
step four: placing the mixed powder prepared in the third step in an atmosphere furnace, firstly introducing inert gas to exhaust oxygen in the furnace, then heating and introducing hydrogen to carry out reduction, and after the cracking temperature is reached, closing the hydrogen; and introducing inert gas to bring ethanol or methanol into the atmosphere furnace, preserving the heat for a period of time, and naturally cooling to room temperature under the atmosphere condition to obtain the metal-doped two-dimensional carbon nitride nanosheet/carbon nanotube multilevel structure.
The heat treatment temperature in the first step is 540-580 ℃, the heating rate is 5-10 ℃/min, and the heat preservation time is 2-6 h.
The first thermal etching temperature in the second step is 500-520 ℃, the heating rate is 10-15 ℃/min, and the heat preservation time is 1-3 h; the temperature of the second thermal etching is 540-560 ℃, the heating rate is 10-15 ℃/min, and the heat preservation time is 1-3 h.
The ferric salt in the third step is one of ferric nitrate, ferric chloride, ferric ammonium citrate, ferric stearate, ferric tartrate, ferric ammonium oxalate hydrate, ferrous chloride, ferric phosphate or ferric sulfate; the nickel salt is one of nickel nitrate, nickel chloride, nickel carbonate, nickel stearate, nickel hypophosphite or nickel sulfate; the cobalt salt is one of cobalt nitrate, cobalt chloride, cobalt acetate, cobalt oxalate, cobalt carbonate, cobalt stearate, cobalt phosphate or cobalt sulfate; the mass ratio of the iron salt, the nickel salt and the cobalt salt to the water or the ethanol is 1.
The mass ratio of the two-dimensional carbon nitride nanosheet to the iron salt, the nickel salt and the cobalt salt in the third step is 1-10.
The hydrogen reduction temperature in the fourth step is 450-500 ℃, the heating rate is 10-15 ℃/min, the heat preservation time is 1-2 h, and the flow rate is 30-60 mL/min.
And the ethanol or the methanol in the fourth step is carried by nitrogen or argon to enter an atmosphere furnace, the cracking temperature is 480-500 ℃, the heating rate is 10-15 ℃/min, the heat preservation time is 1-2 h, and the flow rate is 10-80 mL/min.
The metal-doped two-dimensional carbon nitride nanosheet/carbon nanotube product prepared by the method is characterized in that: the specific surface area of the product is 352-435 m 2 The diameter of the carbon nano tube is 18-30 nm, the length of the carbon nano tube is 80-600 nm, and the resistance is 1.8-6 multiplied by 10 3 Ω。
The invention has the beneficial effects that: the method for preparing the carbon nano tube by catalytically cracking ethanol or methanol and the like is a method with simple process and high yield. The N atom in the two-dimensional carbon nitride nanosheet has six lone-pair electrons, so that a nearly perfect site is provided for anchoring of metal ions or atoms. In addition, the negatively charged N atoms and metal ions form strong interaction, so that the metal ions or atoms are easily captured by the two-dimensional carbon nitride nanosheets. Therefore, in the catalytic cracking process, the reduced metal particles anchored on the surfaces of the carbon nitride nanosheets are used as cracking centers to synthesize the carbon nanotubes, so that the in-situ generated carbon nanotubes are firmly fixed on the surfaces of the two-dimensional carbon nitride nanosheets. Through the technology of the invention, the following aims can be achieved: firstly, the proportion of the carbon nitride nanosheet to the metal salt can be simply regulated and controlled, so that the density of the carbon nanotube on the surface of the carbon nanotube can be regulated and controlled. Secondly, the multilevel structural feature of the in-situ construction has extremely low interface resistance, the contact tightness degree between interfaces is an important factor influencing the migration of electrons or holes, the tight interface contact can effectively reduce the charge transfer resistance, promote the charge transmission and improve the separation efficiency of photo-generated electrons and holes, thereby improving the photocatalytic activity of the photocatalyst; thirdly, the multilevel structure has larger specific surface area, so that the multilevel structure has richer catalytic active sites, reaction areas and adsorption areas for target objects; fourthly, the uniqueness of the multilevel structure endows the two-dimensional carbon nitride nanosheet/carbon nanotube with a multi-level transmission and migration channel of photon-generated carriers, and is beneficial to promoting the separation of electrons and holes; fifthly, the carbon nanotubes generated in situ on the two-dimensional carbon nitride nanosheet have the characteristic of directional arrangement, and compared with a mechanically mixed composite photocatalyst, the carbon nanotubes endow electrons with directional transmission, so that the recombination probability of photo-generated electrons and holes is further reduced; sixthly, in the high-temperature catalytic cracking process, a small part of metal elements can enter the two-dimensional carbon nitride crystal lattice, so that the electronic structure and the energy band structure of the two-dimensional carbon nitride can be regulated and controlled, and the visible light absorption range is widened.
The metal-doped two-dimensional carbon nitride nanosheet/carbon nanotube obtained by the method has unique multi-level nanostructure characteristics (two-dimensional/one-dimensional) and large specific surface area (352-435 m) 2 (g), good microscopic morphology (diameter of carbon nanotubes is 18 to 30nm, length of carbon nanotubes is 80 to 600 nm) and low electrical resistance (1.8 x 10) 3 ～6×10 3 Ω）。
The method is characterized by comprising the following steps:
a. the raw material source is rich and the cost is low;
b. the preparation process is simple and efficient, and the operation is simple and convenient;
c. the in-situ construction of the metal-doped two-dimensional carbon nitride nanosheet/carbon nanotube multilevel nanostructure is beneficial to providing a multi-channel carrier transmission channel, creating a close contact interface and a wide visible light absorption range;
d. the diameter, the length and the density of the carbon nano tube are easy to regulate and control, and the two-dimensional carbon nitride nano sheet/carbon nano tube multistage nano structure with different diameters, lengths and densities can be obtained by simply changing the proportion of the salt solution to the two-dimensional carbon nitride nano sheet, the cracking temperature, the cracking time and the like.
Drawings
FIG. 1 is a metal-doped two-dimensional carbon nitride nanosheet/carbon nanotube multilevel structure after catalytic cracking of example 1;
FIG. 2 is a scanning electron microscope image of the product obtained in example 1;
FIG. 3 is a high power scanning electron microscope image of the product obtained in example 1;
FIG. 4 is a low power transmission electron micrograph of the product obtained in example 1;
FIG. 5 is a high power transmission electron microscope image of the product obtained in example 1.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
Example 1
Putting melamine into a ceramic or quartz crucible, placing the crucible in a muffle furnace for heat treatment, heating to 540 ℃ at a heating rate of 5 ℃/min, and preserving heat for 4 hours to obtain yellow bulk-phase carbon nitride; grinding the synthesized powder into powder, placing the powder on a ceramic flat plate, spreading the powder as far as possible to increase the contact area of the powder and air, and carrying out thermal etching twice, wherein the first thermal etching temperature is 500 ℃, the heating rate is 10 ℃/min, and the heat preservation time is 2h; after cooling, continuing the second thermal etching at 540 ℃, wherein the heating rate is 15 ℃/min, and the heat preservation time is 1h, so as to obtain a faint yellow two-dimensional carbon nitride nanosheet; then, adding 100mg of two-dimensional carbon nitride nanosheets into 50g of 0.2wt% nickel nitrate aqueous solution for ultrasonic treatment, fully and uniformly stirring, and drying; then, placing the dried mixed powder in an atmosphere furnace, evacuating oxygen in the furnace, continuously introducing hydrogen at a heating rate of 10 ℃/min at a flow rate of 30mL/min, and closing the hydrogen after the reduction temperature reaches 500 ℃ and the heat is preserved for 2 hours; and carrying the ethanol into an atmosphere furnace by inert gas, wherein the flow rate is 40mL/min, the cracking temperature is 500 ℃, the temperature is kept for 1h, and then, the ethanol is naturally cooled to the room temperature under the atmosphere condition to obtain the nickel-doped two-dimensional carbon nitride nanosheet/carbon nanotube multilevel structure.
Using scanning electron microscopy and transmissionThe electron microscope technology is used for characterizing the synthesized nickel-doped two-dimensional carbon nitride nanosheet/carbon nanotube multi-level structure, the diameter of the carbon nanotube is 18nm, the length of the carbon nanotube is about 200nm, and the specific surface area of the nickel-doped two-dimensional carbon nitride nanosheet/carbon nanotube multi-level structure obtained by a specific surface area determinator is 435m 2 The resistance of the nickel-doped two-dimensional carbon nitride nanosheet/carbon nanotube multi-level structure is 1.8 multiplied by 10 measured by electrochemical impedance spectroscopy 3 Ω。
Fig. 1 shows that the product obtained after catalytic cracking, i.e., the nickel-doped two-dimensional carbon nitride nanosheet/carbon nanotube multi-level structure, is dark black in color, indicating that a carbon-containing substance is generated. Fig. 2 is a scanning electron micrograph of the obtained product, in which it can be seen that a layer of carbon nanotubes grows on the surface of the layered two-dimensional carbon nitride, and a large number of nanotubes are crosslinked with each other and are in close contact with the two-dimensional carbon nitride nanosheets. FIG. 3 is a high-power scanning electron micrograph of the resulting product, from which it can be further found that the carbon nanotubes have a relatively uniform size and morphology. Fig. 4 is a low-power transmission electron micrograph of the obtained product, which can more clearly show that a large amount of one-dimensional structural substances exist in the carbon nitride nanosheet, and fig. 5 is a high-power transmission electron micrograph of the obtained product, which can obviously observe that the one-dimensional structure of the carbon nanotube is hollow.
Example 2
Putting melamine into a ceramic or quartz crucible, placing the crucible in a muffle furnace for heat treatment, heating to 540 ℃ at a heating rate of 5 ℃/min, and preserving heat for 4 hours to obtain yellow bulk-phase carbon nitride; grinding the synthesized powder into powder, placing the powder on a ceramic flat plate, spreading the powder as far as possible to increase the contact area of the powder and air, and carrying out thermal etching twice, wherein the first thermal etching temperature is 500 ℃, the heating rate is 10 ℃/min, and the heat preservation time is 2h; after cooling, continuing the second thermal etching at 540 ℃, wherein the heating rate is 15 ℃/min, and the heat preservation time is 1h, so as to obtain a faint yellow two-dimensional carbon nitride nanosheet; then, 200mg of two-dimensional carbon nitride nanosheets are added into 50g of 0.2wt% nickel nitrate aqueous solution for ultrasonic treatment, fully and uniformly stirred and dried; then, placing the dried mixed powder in an atmosphere furnace, evacuating oxygen in the furnace, continuously introducing hydrogen at a heating rate of 10 ℃/min and a flow of 60mL/min, and after the reduction temperature reaches 450 ℃ and the temperature is kept for 1h, closing the hydrogen; carrying the ethanol into an atmosphere furnace by inert gas, then carrying out natural cooling to room temperature under the atmosphere condition after the temperature rise rate is 10 ℃/min, the flow rate is 80mL/min and the cracking temperature is 500 ℃ and the temperature is kept for 2h, and obtaining the nickel-doped two-dimensional carbon nitride nanosheet/carbon nanotube multi-stage structure.
The scanning electron microscope and transmission electron microscope technology are utilized to characterize the synthesized nickel-doped two-dimensional carbon nitride nanosheet/carbon nanotube multilevel structure, the diameter of the carbon nanotube is 30nm, the length of the carbon nanotube is approximately 600nm, and the specific surface area of the nickel-doped two-dimensional carbon nitride nanosheet/carbon nanotube multilevel structure obtained by a specific surface area determinator is 410m 2 The resistance of the nickel-doped two-dimensional carbon nitride nanosheet/carbon nanotube multi-level structure is measured to be 6 multiplied by 10 through electrochemical impedance spectroscopy 3 Ω。
Example 3
Putting melamine into a ceramic or quartz crucible, placing the crucible in a muffle furnace for heat treatment, heating to 580 ℃ at a heating rate of 10 ℃/min, and preserving heat for 3h to obtain yellow bulk-phase carbon nitride; grinding the synthesized powder into powder, placing the powder on a ceramic flat plate, spreading the powder as far as possible to increase the contact area of the powder and air, and carrying out thermal etching twice, wherein the first thermal etching temperature is 520 ℃, the heating rate is 15 ℃/min, and the heat preservation time is 1h; cooling, and continuing the second thermal etching at 550 ℃, at a heating rate of 15 ℃/min and for 2h to obtain a light yellow two-dimensional carbon nitride nanosheet; then, adding 1000mg of two-dimensional carbon nitride nanosheets into 50g of nickel chloride aqueous solution with the concentration of 0.2wt%, performing ultrasonic treatment, fully and uniformly stirring, and drying; then, placing the dried mixed powder in an atmosphere furnace, evacuating oxygen in the furnace, continuously introducing hydrogen at a heating rate of 10 ℃/min at a flow rate of 60mL/min, and closing the hydrogen after the reduction temperature reaches 480 ℃ and the heat is preserved for 1h; and carrying the ethanol into an atmosphere furnace by inert gas, then carrying out natural cooling to room temperature under the atmosphere condition after the temperature rise rate is 15 ℃/min, the flow rate is 40mL/min and the cracking temperature is 500 ℃ and the temperature is kept for 2h, so as to obtain the two-dimensional carbon nitride nanosheet/carbon nanotube multi-stage structure.
The scanning electron microscope and transmission electron microscope technology are utilized to characterize the synthesized nickel-doped two-dimensional carbon nitride nanosheet/carbon nanotube multilevel structure, the diameter of the carbon nanotube is confirmed to be 25nm, the length of the carbon nanotube is approximately 100nm, and the specific surface area of the nickel-doped two-dimensional carbon nitride nanosheet/carbon nanotube multilevel structure obtained by a specific surface area determinator is 409m 2 The resistance of the nickel-doped two-dimensional carbon nitride nanosheet/carbon nanotube multi-level structure is 3.3 multiplied by 10 measured by electrochemical impedance spectroscopy 3 Ω。
Example 4
Putting melamine into a ceramic or quartz crucible, placing the crucible in a muffle furnace for heat treatment, heating to 580 ℃ at a heating rate of 10 ℃/min, and preserving heat for 3h to obtain yellow bulk-phase carbon nitride; grinding the synthesized powder into powder, placing the powder on a ceramic flat plate, spreading the powder as far as possible to increase the contact area of the powder and air, and carrying out thermal etching twice, wherein the first thermal etching temperature is 520 ℃, the heating rate is 15 ℃/min, and the heat preservation time is 1h; cooling, and continuing the second thermal etching at 550 ℃, with the heating rate of 15 ℃/min and the heat preservation time of 1h to obtain a light yellow two-dimensional carbon nitride nanosheet; then, adding 200mg of two-dimensional carbon nitride nanosheets into 50g of 0.2wt% ferric nitrate aqueous solution, performing ultrasonic treatment, fully and uniformly stirring, and drying; then, placing the dried mixed powder in an atmosphere furnace, evacuating oxygen in the furnace, continuously introducing hydrogen at a heating rate of 10 ℃/min at a flow rate of 40mL/min, and closing the hydrogen after the reduction temperature reaches 500 ℃ and the heat is preserved for 1h; carrying the ethanol into an atmosphere furnace by inert gas, then carrying out natural cooling to room temperature under the atmosphere condition after the temperature rise rate is 13 ℃/min, the flow rate is 40mL/min and the cracking temperature is 500 ℃ and the temperature is kept for 1h, and obtaining the iron-doped two-dimensional carbon nitride nanosheet/carbon nanotube multi-stage structure.
The scanning electron microscope and transmission electron microscope technology are utilized to characterize the synthesized iron-doped two-dimensional carbon nitride nanosheet/carbon nanotube multi-level structure, the diameter of the carbon nanotube is confirmed to be 28nm, the length of the carbon nanotube is approximately 350nm, and the iron-doped two-dimensional carbon nitride nanotube is obtained through a specific surface area determinatorThe specific surface area of the rice sheet/carbon nano tube multilevel structure is 360m 2 The resistance of the iron-doped two-dimensional carbon nitride nanosheet/carbon nanotube multi-level structure is measured to be 2.3 multiplied by 10 through electrochemical impedance spectroscopy 3 Ω。
Example 5
Putting melamine into a ceramic or quartz crucible, placing the crucible in a muffle furnace for heat treatment, heating to 580 ℃ at the heating rate of 8 ℃/min, and preserving heat for 6 hours to obtain yellow bulk-phase carbon nitride; grinding the synthesized powder into powder, placing the powder on a ceramic flat plate, spreading the powder as far as possible to increase the contact area of the powder and air, and carrying out thermal etching twice, wherein the first thermal etching temperature is 520 ℃, the heating rate is 10 ℃/min, and the heat preservation time is 1h; after cooling, continuing the second thermal etching at 560 ℃, heating up at 15 ℃/min and keeping the temperature for 1h to obtain a light yellow two-dimensional carbon nitride nanosheet; then, adding 800mg of two-dimensional carbon nitride nanosheets into 50g of 0.2wt% ferric chloride aqueous solution for ultrasonic treatment, fully and uniformly stirring, and drying; then, placing the dried mixed powder in an atmosphere furnace, evacuating oxygen in the furnace, continuously introducing hydrogen at a heating rate of 13 ℃/min at a flow rate of 50mL/min, and closing the hydrogen after the reduction temperature reaches 500 ℃ and the heat is preserved for 1h; and carrying the ethanol into an atmosphere furnace by inert gas, wherein the flow rate is 60mL/min, the cracking temperature is 500 ℃, the temperature is kept for 1h, and then the two-dimensional carbon nitride nanosheet/carbon nanotube multi-level structure is obtained by naturally cooling to the room temperature under the atmosphere condition.
The scanning electron microscope and transmission electron microscope technology are utilized to characterize the synthesized iron-doped two-dimensional carbon nitride nanosheet/carbon nanotube multilevel structure, the diameter of the carbon nanotube is confirmed to be 23nm, the length of the carbon nanotube is approximately 370nm, and the specific surface area of the iron-doped two-dimensional carbon nitride nanosheet/carbon nanotube multilevel structure obtained by a specific surface area determinator is 386m 2 The resistance of the iron-doped two-dimensional carbon nitride nanosheet/carbon nanotube multi-level structure is measured to be 4.1 multiplied by 10 through electrochemical impedance spectroscopy 3 Ω。
Example 6
Placing melamine hydrobromide into a ceramic or quartz crucible, placing the crucible in a muffle furnace for heat treatment, heating to 540 ℃ at a heating rate of 10 ℃/min, and preserving heat for 5 hours to obtain yellow bulk-phase carbon nitride; grinding the synthesized powder into powder, placing the powder on a ceramic flat plate, spreading the powder as far as possible to increase the contact area of the powder and air, and carrying out thermal etching twice, wherein the first thermal etching temperature is 510 ℃, the heating rate is 15 ℃/min, and the heat preservation time is 2h; after cooling, continuing the second thermal etching at 560 ℃, heating up at 15 ℃/min and keeping the temperature for 1h to obtain a light yellow two-dimensional carbon nitride nanosheet; then, adding 400mg of two-dimensional carbon nitride nanosheets into 50g of 0.2wt% cobalt nitrate ethanol solution, performing ultrasonic treatment, fully stirring uniformly, and drying; then, placing the dried mixed powder in an atmosphere furnace, evacuating oxygen in the furnace, continuously introducing hydrogen at a heating rate of 13 ℃/min at a flow rate of 50mL/min, and closing the hydrogen after the reduction temperature reaches 500 ℃ and the heat is preserved for 2 hours; and carrying the ethanol into an atmosphere furnace by inert gas, wherein the flow rate is 70mL/min, the cracking temperature is 500 ℃, the temperature is kept for 2h, and then the two-dimensional carbon nitride nanosheet/carbon nanotube multi-level structure is obtained by naturally cooling to the room temperature under the atmosphere condition.
The synthesized cobalt-doped two-dimensional carbon nitride nanosheet/carbon nanotube multi-level structure is characterized by utilizing the scanning electron microscope and transmission electron microscope technologies, the diameter of the carbon nanotube is 29nm, the length of the carbon nanotube is approximately 560nm, and the specific surface area of the cobalt-doped two-dimensional carbon nitride nanosheet/carbon nanotube multi-level structure obtained by a specific surface area determinator is 432m 2 The resistance of the cobalt-doped two-dimensional carbon nitride nano sheet/carbon nano tube multilevel structure is measured to be 5.3 multiplied by 10 through electrochemical impedance spectroscopy 3 Ω。
Example 7
Putting the cage-shaped phosphate melamine salt into a ceramic or quartz crucible, placing the crucible in a muffle furnace for heat treatment, heating to 540 ℃ at a heating rate of 8 ℃/min, and preserving heat for 5 hours to obtain yellow bulk-phase carbon nitride; grinding the synthesized powder into powder, placing the powder on a ceramic flat plate, spreading the powder as far as possible to increase the contact area of the powder and air, and carrying out thermal etching twice, wherein the first thermal etching temperature is 500 ℃, the heating rate is 10 ℃/min, and the heat preservation time is 2h; after cooling, continuing the second thermal etching at 540 ℃, wherein the heating rate is 15 ℃/min, and the heat preservation time is 1h, so as to obtain a faint yellow two-dimensional carbon nitride nanosheet; then, adding 500mg of two-dimensional carbon nitride nanosheets into 50g of nickel sulfate aqueous solution with the concentration of 0.2wt%, performing ultrasonic treatment, fully and uniformly stirring, and drying; then, placing the dried mixed powder in an atmosphere furnace, evacuating oxygen in the furnace, continuously introducing hydrogen at a heating rate of 15 ℃/min at a flow rate of 60mL/min, and closing the hydrogen after the reduction temperature reaches 500 ℃ and the heat is preserved for 2 hours; and carrying the ethanol into an atmosphere furnace by inert gas, wherein the flow rate is 70mL/min, the cracking temperature is 500 ℃, the temperature is kept for 1h, and then, the ethanol is naturally cooled to the room temperature under the atmosphere condition to obtain the nickel-doped two-dimensional carbon nitride nanosheet/carbon nanotube multilevel structure.
The scanning electron microscope and transmission electron microscope technology are utilized to characterize the synthesized nickel-doped two-dimensional carbon nitride nanosheet/carbon nanotube multilevel structure, the diameter of the carbon nanotube is confirmed to be 24nm, the length of the carbon nanotube is approximately 358nm, and the specific surface area of the nickel-doped two-dimensional carbon nitride nanosheet/carbon nanotube multilevel structure obtained by a specific surface area determinator is 400m 2 The resistance of the nickel-doped two-dimensional carbon nitride nanosheet/carbon nanotube multi-level structure is measured to be 4.6 multiplied by 10 through electrochemical impedance spectroscopy 3 Ω。
Example 8
Putting melamine cyanurate into a ceramic or quartz crucible, placing the crucible in a muffle furnace for heat treatment, heating to 550 ℃ at a heating rate of 5 ℃/min, and preserving heat for 4 hours to obtain yellow bulk-phase carbon nitride; grinding the synthesized powder into powder, placing the powder on a ceramic flat plate, spreading the powder as far as possible to increase the contact area of the powder and air, and carrying out thermal etching twice, wherein the first thermal etching temperature is 500 ℃, the heating rate is 10 ℃/min, and the heat preservation time is 1h; after cooling, continuing the second thermal etching at 540 ℃, wherein the heating rate is 15 ℃/min, and the heat preservation time is 1h, so as to obtain a faint yellow two-dimensional carbon nitride nanosheet; then, adding 100mg of two-dimensional carbon nitride nanosheets into 50g of 0.2wt% ferric nitrate ethanol solution, performing ultrasonic treatment, fully and uniformly stirring, and drying; then, placing the dried mixed powder in an atmosphere furnace, evacuating oxygen in the furnace, continuously introducing hydrogen at a heating rate of 10 ℃/min at a flow rate of 50mL/min, and closing the hydrogen after the reduction temperature reaches 500 ℃ and the heat is preserved for 2 hours; and carrying the ethanol into an atmosphere furnace by inert gas, wherein the flow rate is 60mL/min, the cracking temperature is 500 ℃, the temperature is kept for 1h, and then, the ethanol is naturally cooled to the room temperature under the atmosphere condition to obtain the iron-doped two-dimensional carbon nitride nanosheet/carbon nanotube multilevel structure.
The scanning electron microscope and transmission electron microscope technology are utilized to characterize the synthesized iron-doped two-dimensional carbon nitride nano sheet/carbon nano tube multilevel structure, the diameter of the carbon nano tube is confirmed to be 22nm, the length of the carbon nano tube is approximately 480nm, and the specific surface area of the iron-doped two-dimensional carbon nitride nano sheet/carbon nano tube multilevel structure obtained by a specific surface area determinator is 390m 2 The resistance of the iron-doped two-dimensional carbon nitride nanosheet/carbon nanotube multi-level structure is measured to be 2.6 multiplied by 10 through electrochemical impedance spectroscopy 3 Ω。
Example 9
Placing melamine and melamine hydrobromide into a ceramic or quartz crucible, placing the crucible in a muffle furnace for heat treatment, heating to 540 ℃ at a heating rate of 5 ℃/min, and preserving heat for 4 hours to obtain yellow bulk-phase carbon nitride; grinding the synthesized powder into powder, placing the powder on a ceramic flat plate, spreading the powder as far as possible to increase the contact area of the powder and air, and carrying out thermal etching twice, wherein the first thermal etching temperature is 500 ℃, the heating rate is 15 ℃/min, and the heat preservation time is 1h; cooling, and continuing the second thermal etching at 540 ℃, wherein the heating rate is 10 ℃/min, and the heat preservation time is 1h to obtain a faint yellow two-dimensional carbon nitride nanosheet; then, adding 100mg of two-dimensional carbon nitride nanosheets into 50g of 0.2wt% nickel nitrate aqueous solution for ultrasonic treatment, fully and uniformly stirring, and drying; then, placing the dried mixed powder in an atmosphere furnace, evacuating oxygen in the furnace, continuously introducing hydrogen at a heating rate of 10 ℃/min at a flow rate of 30mL/min, and closing the hydrogen after the reduction temperature reaches 500 ℃ and the heat is preserved for 2 hours; and carrying the ethanol into an atmosphere furnace by inert gas, wherein the flow rate is 20mL/min, the cracking temperature is 500 ℃, the temperature is kept for 1h, and then, the ethanol is naturally cooled to the room temperature under the atmosphere condition to obtain the nickel-doped two-dimensional carbon nitride nanosheet/carbon nanotube multilevel structure.
By usingThe scanning electron microscope and transmission electron microscope technology are used for characterizing the synthesized nickel-doped two-dimensional carbon nitride nanosheet/carbon nanotube multi-level structure, the diameter of the carbon nanotube is 21nm, the length of the carbon nanotube is approximately 261nm, and the specific surface area of the nickel-doped two-dimensional carbon nitride nanosheet/carbon nanotube multi-level structure obtained by a specific surface area determinator is 426m 2 The resistance of the nickel-doped two-dimensional carbon nitride nano sheet/carbon nano tube multilevel structure is measured to be 2.0 multiplied by 10 through electrochemical impedance spectroscopy 3 Ω。
The foregoing embodiments are illustrative only of the principles and utilities of the present invention, as well as some embodiments, and are not intended to limit the invention; it should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the inventive concept of the present invention, and these changes and modifications belong to the protection scope of the present invention.
Claims (8)
1. A method for constructing a metal-doped two-dimensional carbon nitride nanosheet/carbon nanotube multilevel structure in situ is characterized by comprising the following steps:
the method comprises the following steps: putting one or more of melamine, melamine hydrobromide, cage-shaped phosphate melamine salt and melamine cyanurate into a ceramic or quartz crucible, and carrying out heat treatment to obtain bulk-phase carbon nitride;
step two: thermally etching the bulk carbon nitride prepared in the step one twice to obtain two-dimensional carbon nitride nanosheets;
step three: uniformly mixing the two-dimensional carbon nitride nanosheets prepared in the second step with ferric salt, nickel salt, cobalt salt aqueous solution or ethanol solution with certain concentration, and drying to obtain mixed powder;
step four: placing the mixed powder prepared in the third step in an atmosphere furnace, firstly introducing inert gas to evacuate oxygen in the furnace, then heating and introducing hydrogen to reduce, and after the cracking temperature is reached, closing the hydrogen; and introducing inert gas to bring ethanol or methanol into the atmosphere furnace, preserving the heat for a period of time, and naturally cooling to room temperature under the atmosphere condition to obtain the metal-doped two-dimensional carbon nitride nanosheet/carbon nanotube multilevel structure.
2. The method of claim 1, wherein: the heat treatment temperature in the first step is 540-580 ℃, the heating rate is 5-10 ℃/min, and the heat preservation time is 2-6 h.
3. The method of claim 1, wherein: the first thermal etching temperature in the second step is 500-520 ℃, the heating rate is 10-15 ℃/min, and the heat preservation time is 1-3 h; the temperature of the second thermal etching is 540-560 ℃, the heating rate is 10-15 ℃/min, and the heat preservation time is 1-3 h.
4. The method of claim 1, wherein: the ferric salt in the third step is one of ferric nitrate, ferric chloride, ferric ammonium citrate, ferric stearate, ferric tartrate, ferric ammonium oxalate hydrate, ferrous chloride, ferric phosphate or ferric sulfate; the nickel salt is one of nickel nitrate, nickel chloride, nickel carbonate, nickel stearate, nickel hypophosphite or nickel sulfate; the cobalt salt is one of cobalt nitrate, cobalt chloride, cobalt acetate, cobalt oxalate, cobalt carbonate, cobalt stearate, cobalt phosphate or cobalt sulfate; the mass ratio of the iron salt, the nickel salt and the cobalt salt to the water or the ethanol is 1.
5. The method of claim 1, wherein: the mass ratio of the two-dimensional carbon nitride nanosheet to the iron salt, the nickel salt and the cobalt salt in the third step is 1.
6. The method of claim 1, wherein: the hydrogen reduction temperature in the fourth step is 450-500 ℃, the heating rate is 10-15 ℃/min, the heat preservation time is 1-2 h, and the flow rate is 30-60 mL/min.
7. The method as claimed in claim 1, wherein the ethanol or methanol in the fourth step is carried into the atmosphere furnace by nitrogen or argon, the cracking temperature is 480-500 ℃, the heating rate is 10-15 ℃/min, the holding time is 1-2 h, and the flow rate is 10-80 mL/min.
8. The metal-doped two-dimensional carbon nitride nanosheet/carbon nanotube article made by the method of claim 1, wherein: the specific surface area of the product is 352-435 m 2 The diameter of the carbon nano tube is 18-30 nm, the length of the carbon nano tube is 80-600 nm, and the resistance is 1.8-6 multiplied by 10 3 Ω。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211257820.XA CN115845893B (en) | 2022-10-14 | 2022-10-14 | Method for in-situ construction of metal-doped two-dimensional carbon nitride nano sheet/carbon nano tube multi-stage structure and product thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211257820.XA CN115845893B (en) | 2022-10-14 | 2022-10-14 | Method for in-situ construction of metal-doped two-dimensional carbon nitride nano sheet/carbon nano tube multi-stage structure and product thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115845893A true CN115845893A (en) | 2023-03-28 |
| CN115845893B CN115845893B (en) | 2024-03-05 |
Family
ID=85661492
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211257820.XA Active CN115845893B (en) | 2022-10-14 | 2022-10-14 | Method for in-situ construction of metal-doped two-dimensional carbon nitride nano sheet/carbon nano tube multi-stage structure and product thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115845893B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105540590A (en) * | 2015-12-17 | 2016-05-04 | 中北大学 | Preparation method of Fe3C nanowire filled and nitrogen doped carbon nanotube composite with high specific surface area |
| CN110002414A (en) * | 2019-03-22 | 2019-07-12 | 张家港市东大工业技术研究院 | A kind of preparation method of nitride porous carbon nanotube |
| CN110773217A (en) * | 2019-09-24 | 2020-02-11 | 嘉兴学院 | Preparation method of nitrogen-doped carbon nanotube material containing transition metal |
| CN111129510A (en) * | 2019-12-16 | 2020-05-08 | 江苏大学 | Preparation method and application of carbon material modified graphite phase carbon nitride nanosheet loaded platinum nano electro-catalyst |
| CN111710880A (en) * | 2020-06-30 | 2020-09-25 | 周华模 | Fe3C loaded Cu doped g-C3N4Oxygen reduction catalyst and process for producing the same |
| CN113042084A (en) * | 2021-03-25 | 2021-06-29 | 华东理工大学 | Preparation method and application of manganese oxide composite carbon nitride nanotube composite photocatalyst |
| CN114054066A (en) * | 2021-11-30 | 2022-02-18 | 江苏大学 | Doped g-C3N4Nanotube photocatalyst, preparation method and application |
-
2022
- 2022-10-14 CN CN202211257820.XA patent/CN115845893B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105540590A (en) * | 2015-12-17 | 2016-05-04 | 中北大学 | Preparation method of Fe3C nanowire filled and nitrogen doped carbon nanotube composite with high specific surface area |
| CN110002414A (en) * | 2019-03-22 | 2019-07-12 | 张家港市东大工业技术研究院 | A kind of preparation method of nitride porous carbon nanotube |
| CN110773217A (en) * | 2019-09-24 | 2020-02-11 | 嘉兴学院 | Preparation method of nitrogen-doped carbon nanotube material containing transition metal |
| CN111129510A (en) * | 2019-12-16 | 2020-05-08 | 江苏大学 | Preparation method and application of carbon material modified graphite phase carbon nitride nanosheet loaded platinum nano electro-catalyst |
| CN111710880A (en) * | 2020-06-30 | 2020-09-25 | 周华模 | Fe3C loaded Cu doped g-C3N4Oxygen reduction catalyst and process for producing the same |
| CN113042084A (en) * | 2021-03-25 | 2021-06-29 | 华东理工大学 | Preparation method and application of manganese oxide composite carbon nitride nanotube composite photocatalyst |
| CN114054066A (en) * | 2021-11-30 | 2022-02-18 | 江苏大学 | Doped g-C3N4Nanotube photocatalyst, preparation method and application |
Non-Patent Citations (5)
| Title |
|---|
| PAWAR, RC ET AL.: "In situ reduction and exfoloation of g-C3N4 nanosheets with copious active sites via a thermal approach for effective water splitting", 《CATALYSIS SCIENCE & TECHNOLOGY》, vol. 9, no. 4, 21 February 2019 (2019-02-21), pages 1004 - 1012 * |
| YANG GANG ET AL.: "One-Step Chemical Vapor Decomposition Synthesis of Hierarchical Ni and N Co-Doped Carbon Nanosheets/Nanotube Hybrids for Efficient Electrochemical CO2 Reduction at Commercially Viable Current Densities", 《ACS CATALYSIS》, vol. 11, no. 16, 4 August 2021 (2021-08-04), pages 10333 - 10344 * |
| YONGZHI YU ET AL.: "Self-assembly of Yolk-shell porous Fe-doped g-C3N4 microarchitectures with excellent photocatalytic performance under visible light", 《SUSTAINABLE MATERIALS AND TECHNOLOGIES》, vol. 17, 31 December 2018 (2018-12-31), pages 1 - 8 * |
| 刘灿群等: "FeCo/氮化碳（g-C3N4）光催化剂的制备及其性能研究", 《科学技术创新》, no. 29, 15 October 2022 (2022-10-15), pages 175 - 178 * |
| 宋玉祥: "氮化碳基纳米催化剂的合成与性质研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》, no. 3, 15 March 2022 (2022-03-15), pages 016 - 1453 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115845893B (en) | 2024-03-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102886270B (en) | SiC is nanocrystalline/Graphene hetero-junctions and preparation method and application | |
| CN107456991B (en) | g-C3N4Preparation method of quantum dot supported bismuth tungstate nanosheet photocatalyst | |
| Zhang et al. | g‐C3N4 nanosheet nanoarchitectonics: H2 generation and CO2 reduction | |
| CN105396606A (en) | Cerium oxide, graphene quantum dots and graphene-like phase carbon nitride composite photoactivate material and preparation method thereof | |
| CN107268024B (en) | Compound α type iron oxide vermiform nano-structure array light anode of cobaltosic oxide and its preparation method and application | |
| WO2021232751A1 (en) | Porous coo/cop nanotubes, preparation method therefor and use thereof | |
| CN107983387B (en) | Preparation method and application of carbon nitride/bismuth selenate composite material | |
| CN113145138B (en) | Thermal response type composite photocatalyst and preparation method and application thereof | |
| CN110467162B (en) | Novel graphite-phase carbon nitride polymer material and preparation method and application thereof | |
| KR20210157765A (en) | Three-dimensional hollow-sphere nano architecture, Photocatalytic comprising thereof and preparing methods thereof | |
| CN112473712A (en) | CeO treated with different atmospheres2/g-C3N4Heterojunction material, preparation method and application thereof | |
| CN112791730A (en) | Z-type nano-copper vanadate-based composite photocatalyst and preparation method and application thereof | |
| Xu et al. | Synthesis of crystalline g-C3N4 with rock/molten salts for efficient photocatalysis and piezocatalysis | |
| CN104923263A (en) | Composite photocatalytic water splitting catalyst and preparation method thereof | |
| CN110694606B (en) | Universal method for preparing multi-level pore coexisting heteroatom-doped carbon catalyst by using soft template agent and application thereof | |
| CN108285143A (en) | A kind of preparation method of biomass-based N doping thin layer graphite carbon material | |
| CN115920929B (en) | MoO3-x/Cu0.5Cd0.5S composite photocatalyst, preparation method and application | |
| CN114100682B (en) | Lupin She Yizhi junction photocatalyst and preparation method thereof | |
| CN116689006A (en) | Carbon nitride nano-sheet composite material and preparation method and application thereof | |
| CN115845893B (en) | Method for in-situ construction of metal-doped two-dimensional carbon nitride nano sheet/carbon nano tube multi-stage structure and product thereof | |
| CN115090318B (en) | Preparation method and application of high specific surface area intermolecular heterojunction carbon nitride photocatalyst | |
| CN112675832B (en) | Carbon dioxide reduction ordered mesoporous catalytic material and preparation method thereof | |
| CN111807336B (en) | Amorphous molybdenum oxide nanodot/two-dimensional carbon nitride nanosheet with photocatalysis and photothermal conversion performances and preparation method thereof | |
| CN113277514A (en) | Transition metal carbide Mo2Preparation method of material C | |
| CN109985652B (en) | Photocatalyst and preparation method and application thereof |
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 |