CN106315531A - Black phosphorus modified by aromatic compound and preparation method and application thereof - Google Patents
Black phosphorus modified by aromatic compound and preparation method and application thereof Download PDFInfo
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- CN106315531A CN106315531A CN201610707744.6A CN201610707744A CN106315531A CN 106315531 A CN106315531 A CN 106315531A CN 201610707744 A CN201610707744 A CN 201610707744A CN 106315531 A CN106315531 A CN 106315531A
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- black phosphorus
- aromatic compound
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- phosphorus
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 173
- 150000001491 aromatic compounds Chemical class 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 11
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 239000012954 diazonium Substances 0.000 claims abstract description 7
- 238000007626 photothermal therapy Methods 0.000 claims abstract description 7
- 239000012769 display material Substances 0.000 claims abstract description 6
- 239000010409 thin film Substances 0.000 claims abstract description 4
- -1 nitro, hydroxyl Chemical group 0.000 claims description 33
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 230000003287 optical effect Effects 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 238000002560 therapeutic procedure Methods 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 150000003217 pyrazoles Chemical class 0.000 claims description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 150000003457 sulfones Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 18
- 125000004437 phosphorous atom Chemical group 0.000 abstract description 13
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 239000010406 cathode material Substances 0.000 abstract 1
- 150000001989 diazonium salts Chemical class 0.000 abstract 1
- 238000002428 photodynamic therapy Methods 0.000 abstract 1
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 20
- 0 C*c1ccc(*C)cc1 Chemical compound C*c1ccc(*C)cc1 0.000 description 12
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 12
- 239000012298 atmosphere Substances 0.000 description 10
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 10
- 229910052698 phosphorus Inorganic materials 0.000 description 10
- 239000011574 phosphorus Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 4
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241001263092 Alchornea latifolia Species 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 241000316887 Saissetia oleae Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000005779 cell damage Effects 0.000 description 1
- 208000037887 cell injury Diseases 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 231100000433 cytotoxic Toxicity 0.000 description 1
- 230000001472 cytotoxic effect Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 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
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000037351 starvation Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/0052—Thermotherapy; Hyperthermia; Magnetic induction; Induction heating therapy
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/0057—Photodynamic therapy with a photosensitizer, i.e. agent able to produce reactive oxygen species upon exposure to light or radiation, e.g. UV or visible light; photocleavage of nucleic acids with an agent
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/02—Preparation of phosphorus
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
Abstract
The invention provides black phosphorus modified by an aromatic compound and a preparation method and application thereof. The black phosphorus modified by the aromatic compound is a product obtained by combining black phosphorus and an aromatic group through a P-C covalent bond. The method comprises the step of performing reaction on diazonium salt of the aromatic compound and a black phosphorus raw material to prepare the black phosphorus modified by the aromatic compound. The application comprises preparation of a thin film transistor material, a cathode material of a battery, a flexible display material, an LED material, a photo-switch material, a biosensor material, a photodynamic therapy reagent and a photo-thermal therapy reagent from the modified black phosphorus. Based on lone pair electrons, the aromatic compound is coupled to the surface of the black phosphorus in a P-C covalent binding way, and the generation of a P-C bond occupies the lone pair electrons of phosphorus atoms, so that the phosphorus atoms lose the capacity of oxidization reaction; and meanwhile, by the existence of an aromatic nucleus, the black phosphorus can be protected, so that the stability of the black phosphorus is kept.
Description
Technical field
The present invention relates to black phosphorus and preparation method and application, particularly relate to a kind of black phosphorus modified through aromatic compound
And preparation method and application.
Background technology
Two-dimensional material is study hotspot in recent years, and Typical Representative includes the transition metal two of Graphene and semiconductor property
Sulfide etc..From the beginning of 2014, occurring in that a kind of New Two Dimensional material black phosphorus (Black Phosphorus, BP), it is gathered around
There are variable band-gap energy and good carrier mobility.The same with Graphene, black phosphorus can peel off into monoatomic layer thin slice, this
The black phosphorus planting monolayer is also referred to as black phosphorus alkene.Black phosphorus the aspects such as machinery, electronics, optics, calorifics, acoustics have uniqueness character and
Excellent performance.As a kind of direct band-gap semicondictor material, black phosphorus can replace silicon in the semiconductor industry, can be used for thin film brilliant
The preparation of body pipe, the negative material of battery, flexible display material, LED, photoswitch, optical dynamic therapy reagent, photo-thermal therapy examination
Agent, biosensor etc., just because of these character so that the research of black phosphorus presents explosive growth in these 2 years
(H.O.Churchill,P.Jarillo-Herrero,Nat.Nanotechnol.2014,9,330；L.Li,Y.Yu,G.J.Ye,
Q.Ge,X.Ou,H.Wu,D.Feng,X.H.Chen,Y.Zhang,Nat.Nanotechnol.2014,9,372；J.S.Qiao,
X.H.Kong,Z.X.Hu,F.Yang,W.Ji,NatureCommun.2014,5,4475；D.Xiang,C.Han,J.Wu,
S.Zhong,Y.Y.Liu,J.D.Lin,X.A.Zhang,W.P.Hu,B.A.H.CatroNeto,A.T.Shen
Wee,W.Chen,Nature Commun.2014,6,6485；X.M.Wang,A.M.Jones,K.L.Seyler,V.Tran,
Y.C.Jia,H.Zhao,H.Wang,L.Yang,X.D.Xu,F.N.Xia,Nat.Nanotechnol.2015,10,517；
J.Sun,H.W.Lee,M.Pasta,H.T.Yuan,G.Y.Zheng,Y.M.Sun,Y.Z.Li,Y.Cui,
Nat.Nanotechnol.2015.)。
Black phosphorus is the form that white phosphorus reacts a kind of new phosphorus simple substance of generation at high temperature under high pressure, former with the four of white phosphorus phosphorus
Molecular tetradecahedral crystal structure is different, and the crystal structure of black phosphorus is rearranged at high temperature under high pressure, substantial amounts of phosphorus
Atom is connected with each other, formed a regular array planar structure (H.O.Churchill, P.Jarillo-Herrero,
Nat.Nanotechnol.2014,9,330).In this plane, each phosphorus atoms is all connected with other three phosphorus atoms,
And there is certain bond distance and bond angle；It is packed together by Van der Waals force between plane and plane.
Although having the performance of excellence, but black phosphorus, particularly black phosphorus alkene have a critical defect: unstable in atmosphere,
Expose and the most easily slowly aoxidized by oxygen, generate oxide and the phosphoric acid of phosphorus, cause the disintegration of black phosphorus two-dimensional structure, and
And then affect its function.The mechanism that black phosphorus is oxidized at present has been illustrated: phosphorus atoms easily carries out reaction generate phosphorus with oxygen
Oxide, the oxide of phosphorus and then and air in moisture carry out reaction generate phosphoric acid (A.Favron, E.Gaufres,
F.Fossard,A.L.P.L’Heureux,N.Y.W.Tang,P.L.Lévesque,A.Loiseau,R.Leonelli,
S.Francoeur,R.Martel,Nature Mater.2015,14,826.).The structure of black phosphorus can be caused brokenly by whole process
Bad so that it is to lose the performance at the aspect such as electricity, optics.Therefore, how to solve the problem that black phosphorus is the most oxidized, maintain its structure
With stablizing of performance, become the key issue affecting black phosphorus development.
In order to solve the stability problem of black phosphorus, researchers are by different methods difference on the surface of black phosphorus covers
Material, with starvation and moisture, reduce phosphorus atoms and black phosphorus be placed in silica-based by the touch opportunity of oxygen moisture: Wood et al.
Surface, titanium, gold and the oxide of aluminum on the upper surface of black phosphorus covers successively so that the stability of black phosphorus is strengthened
(J.D.Wood,S.A.Wells,D.Jariwala,K.S.Chen,E.K.Cho,V.K.Sangwan,X.L.Liu,
L.J.Lauhon,T.J.Marks,M.C.Hersam,Nano Lett.2014,14,6964.)；Black phosphorus is placed in three by Kim et al.
The surface of Al 2 O, the upper surface at black phosphorus also covers last layer aluminium sesquioxide simultaneously so that the only phosphorus atoms of side
Could contact with oxygen, and compared with upper and lower surface, the phosphorus atoms quantity of side is little, therefore can improve the stability of black phosphorus
((J.S.Kim,Y.Liu,W.Zhu,S.Kim,D.Wu,L.Tao,A.Dodabalapur,K.Lai,D.Akinwande,
Sci.Rep.2015,5,8989.)；Lee et al. is by the method for atomic deposition nano level titanium dioxide on black phosphorus surface deposits
Titanium, also can improve black phosphorus stability (H.U.Lee, S.C.Lee, J.Won, B.C.Son, S.Choi, Y.Kim, S.Y.Park,
H.S.Kim,Y.C.Lee,J.Lee,Sci.Rep.2015,5,8691.)。
Existing technical scheme, core thinking is to cover other material on the surface of black phosphorus, reduce black phosphorus and oxygen and
The contact of moisture, its effect solving black phosphorus oxidized is not very good, therefore, it is necessary to find new solution black phosphorus quilt
The technical scheme of oxidation.
Summary of the invention
An object of the present invention is to provide a kind of new black phosphorus modified through aromatic compound, to avoid black phosphorus to exist
In air oxidized, keep stablizing of its structure and performance.
Another object of the present invention is to provide the preparation method of a kind of described black phosphorus modified through aromatic compound.
Another object of the present invention is to provide the compositions containing the described black phosphorus modified through aromatic compound.
It is still another object of the present invention to provide the described black phosphorus modified through aromatic compound or the compositions containing it
Application.
For achieving the above object, on the one hand, the present invention provides a kind of black phosphorus modified through aromatic compound, described through virtue
The black phosphorus that fragrant compounds of group is modified is the product that black phosphorus is combined by P-C covalent bond with aromatic group.
According to the detailed description of the invention of the present invention, the black phosphorus structural representation modified through aromatic compound of the present invention
As described in Figure 1.Phosphorus atoms during black ball represents black phosphorus in Fig. 1, it is combined by P-C covalent bond with aromatic group.
According to the detailed description of the invention of the present invention, aromatic group of the present invention is for replacing or the most substituted phenyl.
Preferably, described replacement or the most substituted phenyl have a structure shown in formula (I):
R in formula (I)1～R5It is each independently hydrogen atom, halogen atom, nitro, hydroxyl, C1～6Alkyl, C1～3Alkoxyl；
This C1～6Alkyl is unsubstituted or replaces through one or more (such as 1～3) following group: halogen atom, nitre
Base, hydroxyl, amino, methyl, ethyl, n-pro-pyl；
This C1～3Alkoxyl is unsubstituted or replaces through one or more (such as 1～3) following group: halogen atom, nitre
Base, hydroxyl, amino, methyl, ethyl, n-pro-pyl.
C of the present invention1～6Alkyl is preferably C1～3Alkyl.This C1～3Alkyl is unsubstituted or through one or more (such as 1
～3) replacement of following group: halogen atom, nitro, hydroxyl, amino, methyl, ethyl, n-pro-pyl.
Exemplary substituted C1～3Alkyl includes-CF3。
C of the present invention1～6Alkyl refers to the straight or branched alkyl that carbon number is 1～6, includes but not limited to first
Base, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, sec-amyl, neopentyl, just oneself
Base, isohesyl etc..
C of the present invention1～3Alkyl refers to the straight or branched alkyl that carbon number is 1～3, including methyl, ethyl, just
Propyl group, isopropyl.
C of the present invention1～3Alkoxyl is described C1～3The alkoxyl that alkyl is formed with oxygen.
Halogen of the present invention includes fluorine, chlorine, bromine or iodine, preferably fluorine.
It is highly preferred that described replacement or the most substituted phenyl have a following structure:
As it was previously stated, the black phosphorus of unmodified is unstable in water or air, it is oxidized easily, generates oxide and the phosphorus of phosphorus
Acid, causes the disintegration of black phosphorus structure and the disappearance of performance.The present invention thinks that black phosphorus the most easily reacts with oxygen, is
Because after phosphorus atoms and other three phosphorus atoms bondings, outer layer still has a pair lone pair electrons, and these lone pair electrons are easily by oxygen molecule
Seize, cause the oxidation of black phosphorus.Prior art is not started with from lone pair electrons and is solved the problem of oxidation of black phosphorus, only at black phosphorus table
Face covers other materials upper, and lone pair electrons yet suffer from, and therefore black phosphorus still has oxidized possibility.The present invention is from lone pair electrons
Setting out, on black phosphorus surface with aromatic compound in P-C covalently bound mode coupling, it is former that the generation of P-C key i.e. occupies phosphorus
The lone pair electrons of son, are allowed to lose the ability with oxygen reaction, and black phosphorus also can be played protection and make by the existence of aromatic rings simultaneously
With, thus keep the stability of black phosphorus.
The present invention, from the lone pair electrons of black phosphorus phosphorus atoms, designs in the covalently bound mode of P-C even on black phosphorus surface
Connection aromatic compound, the generation of P-C key occupies the lone pair electrons of phosphorus atoms, forms stable covalent bond, to reach stable
The purpose of phosphorus atoms lone pair electrons, experiment shows that the present invention can keep black phosphorus brilliant through the black phosphorus that aromatic compound is modified very well
Body structure and be greatly enhanced the oxidation resistance of black phosphorus.
On the other hand, the present invention provides the preparation method of a kind of above-mentioned black phosphorus modified through aromatic compound, described system
Preparation Method includes making the diazol of aromatic compound and black phosphorus raw material reaction described to modify through aromatic compound to prepare
The step of black phosphorus.
According to the detailed description of the invention of the present invention, the diazol of aromatic compound of the present invention includes aromatic compound
One or more in the diazonium tetrafluoroborate of thing, pyrazoles diazonium inner salt and three dish alkene diazols.
Exemplarily, the method for the invention reaction as shown in Figure 2 is carried out.The diazonium of the aromatic compound in Fig. 2
Salt is to replace or the diazonium tetrafluoroborate of not substituted benzene, R in figure1～R5As defined above identical with formula (I) of definition.
According to the detailed description of the invention of the present invention, the method for the invention comprises the steps:
Described black phosphorus raw material is dissolved in organic solvent, adds tetra-tert amine hexafluorophosphate and described aromatic compound
The diazol of thing, lucifuge reaction obtains the described black phosphorus modified through aromatic compound；Or
Described black phosphorus raw material is supported in substrate, then makes it containing tetra-tert amine hexafluorophosphate and described virtue
In the organic solvent of the diazol of fragrant compounds of group, lucifuge reaction obtains the described black phosphorus modified through aromatic compound.
Optionally, after having reacted, the organic solvent that reaction can be used to be used washs, and obtain after purification is logical
Cross P-C key and the covalently bound black phosphorus of aromatic compound.
In the method for the invention, described organic solvent includes but not limited to acetonitrile, ethanol, isopropanol, acetone, acetic acid
In ethyl ester, dichloromethane, chloroform, oxolane, N-Methyl pyrrolidone, N,N-dimethylformamide and dimethyl sulfoxide
One or more.
In the method for the invention, described substrate includes but not limited to silicon chip, such as include surface be not coated with by silicon chip,
Surface is coated with by silicon dioxide or the silicon chip etc. of silicon nitride.
In the method for the invention, described tetra-tert amine hexafluorophosphate concentration in reaction system be 0.01～
10mol/L。
In the method for the invention, the diazol of described aromatic compound concentration in reaction system be 0.01～
100mmol/L。
In the method for the invention, described reaction is to react 1～24h at 20～40 DEG C.
In the method for the invention, described black phosphorus raw material concentration in reaction system is 10 μ g/ml～10mg/ml.
If do not conflicted, the technical characteristic in preceding method of the present invention can combination in any, as long as institute of the present invention can be prepared
State the black phosphorus modified through aromatic compound.Such as, described method comprises the steps:
Black phosphorus raw material is dissolved in organic solvent, makes final concentration of 10 μ g/ml～10mg/ml of black phosphorus raw material, be added in
Concentration in reaction system is the tetra-tert amine hexafluorophosphate of 0.01～10mol/L and the concentration in reaction system is
The diazol of the aromatic compound of 0.01～100mmol/L, reacts 1～24h, after having reacted at 20～40 DEG C, use anti-
Answer used organic solvent to wash, obtain the described black phosphorus modified through aromatic compound；Or
The black phosphorus raw material that concentration is 10 μ g/ml～10mg/ml is dissolved in organic solvent, drops in substrate, treat that solvent is certainly
The most dried must be supported on suprabasil black phosphorus raw material, then make it at the tetra-tert amine six that concentration is 0.01～10mol/L
In the organic solvent system of the diazol of fluorophosphate and aromatic compound that concentration is 0.01～100mmol/L, 20～40
Reacting 1～24h, after having reacted at DEG C, the organic solvent using reaction to be used washs, and obtains described through aromatic series
The black phosphorus that compound is modified.
Another further aspect, the present invention provides a kind of compositions, and it contains of the present invention modifies through aromatic compound
Black phosphorus or the black phosphorus modified through aromatic compound prepared by described preparation method.
Another further aspect, the present invention provides the described black phosphorus through aromatic compound modification or by described preparation method system
Through aromatic compound modify black phosphorus or described compositions prepare thin-film-transistor material, the negative material of battery,
In flexible display material, LED material, optical switch material, biosensor material, optical dynamic therapy reagent or photo-thermal therapy reagent
Application.
Thin-film-transistor material of the present invention refers to the material for constructing TFT semiconductors layer.
The negative material of battery of the present invention refers to constitute in battery the material of negative pole.
Flexible display material of the present invention refer to for prepare flexible display apparatus soft, changeable type is flexible
Material.
LED material of the present invention refers to the semi-conducting material for constructing light emitting diode basic structure.
Optical switch material of the present invention refers to the optical signal physics switching that can realize in optical transmission line or integrated optical circuit
Or the semi-conducting material of logical operation.
Optical dynamic therapy reagent of the present invention refers to the material with photodynamic effect.Photodynamic effect is a kind of aerobic
The Photosensitive reaction of the adjoint biological effect that molecule participates in.Its process is, the laser of specific wavelength irradiates the light making tissue resorption
Quick dose is excited, and the photosensitizer of excited state passes to the oxygen of surrounding energy, generates the singlet oxygen that activity is the strongest, singlet
Oxygen and adjacent biomacromolecule generation oxidation reaction, produce cytotoxic effect, and then cause cell damage or even death.
Photo-thermal therapy reagent of the present invention refers to that the material for photo-thermal therapy method, this material have high light heat and turn
Change the material of efficiency, be injected into inside of human body during use so that it is be gathered near tumor tissues, and at the photograph of external light source
Penetrate down and convert light energy into heat energy and carry out treating and such as kill cancerous cell etc..
Biosensor material of the present invention refers to sensitive to biological substance and its concentration can be converted to electricity or light
Signal carries out the material detected.
According to specific embodiments of the present invention, black phosphorus of the present invention or black phosphorus raw material include but not limited to black phosphorus alkene,
Black phosphorus nanometer sheet or black phosphorus crystal, preferably black phosphorus nanometer sheet.
Black phosphorus alkene of the present invention refers to monoatomic layer black phosphorus thin slice.
Black phosphorus nanometer sheet of the present invention refers to more than two atomic layers, the thickness black phosphorus thin slice less than 100nm.
Black phosphorus crystal of the present invention refers to black phosphorus bulk crystals under macroscopic macro-scale.
In sum, the present invention is from the lone pair electrons of black phosphorus phosphorus atoms, with the diazol of aromatic compound and black
Phosphorus reacts, and generates stable P-C covalence key, improves the non-oxidizability of black phosphorus.This black scale can be at thin film transistor (TFT)
Preparation, the negative material of battery, flexible display material, LED, photoswitch, optical dynamic therapy reagent, photo-thermal therapy reagent, life
The fields such as thing sensor have and are more widely applied.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the black phosphorus modified through aromatic compound of the present invention.
Fig. 2 is the exemplary response diagram of the method for the invention.
Fig. 3 is x-ray photoelectron spectroscopy (XPS) figure through the black phosphorus to methoxybenzene modification obtained in embodiment 1.
Fig. 4 a, Fig. 4 b are respectively the most modified black phosphorus nanometer sheet and expose 4 days and 7 days rear surface figures in atmosphere.
Fig. 5 a, Fig. 5 b are respectively the black phosphorus modified through p-nitrophenyl and expose exterior view after 4 days and 7 days in atmosphere.
Fig. 6 a, Fig. 6 b are respectively the black phosphorus modified through p-methoxyphenyl and expose surface after 4 days and 7 days in atmosphere
Figure.
The black phosphorus of the black phosphorus that Fig. 7 a, Fig. 7 b respectively modify through 2,4 dichloro benzene base exposes in atmosphere after 4 days and 7 days
Exterior view.
Fig. 8 a is that 7 days rear surface figures placed by the most modified black phosphorus, and Fig. 8 b is that the black phosphorus through modifying methoxybenzene places 7
It rear surface figure.
Fig. 9 is the black phosphorus transmission electron microscope picture through modifying methoxybenzene.
Figure 10 is through the high-resolution-ration transmission electric-lens to the black phosphorus that methoxybenzene is modified.
Detailed description of the invention
In order to the technical characteristic of the present invention, purpose and beneficial effect are more clearly understood from, in conjunction with being embodied as
Technical scheme is carried out described further below by example and accompanying drawing, it should be understood that these examples be merely to illustrate the present invention and not
For limiting the scope of the present invention.
Embodiment 1
Black phosphorus nanometer sheet being dissolved in acetonitrile solvent so that it is concentration is 100 μ g/ml, being added in concentration in system is 0.5M
Tetra-tert amine hexafluorophosphate and in system concentration be 50mM to methoxybenzene diazonium tetrafluoroborate, keep away at 30 DEG C
Photoreaction 20h, the black phosphorus that centrifugal 10min must modify through p-methoxyphenyl under conditions of 10000rpm.
Carry out elementary analysis (as shown in Figure 3) with the x-ray photoelectron spectroscopy (XPS) product to obtaining, find P elements
Momentum profiles in except the black phosphorus feature P2p peak of about 130eV, near 133eV, have also appeared the characteristic peak of C-P key, and
The peak of nitrogen element disappears, and illustrates that diazol and black phosphorus are successfully made reaction, the carbon atom that phenyl ring was originally connected with diazo
Success and black phosphorus have carried out covalent bond.
Embodiment 2
Be that 20 μ g/ml black phosphorus nanometer sheet are dissolved in acetonitrile by concentration, drop in be not coated with by silicon chip substrate on, natural drying obtains
It is supported on not by the black phosphorus nanometer sheet on the substrate silicon chip being coated with quilt, then makes it at the tetra-tert amine six that system concentration is 0.1M
Lucifuge reaction 15h at 25 DEG C in the acetonitrile solution of fluorophosphate and p-nitrophenyl diazonium tetrafluoroborate that system concentration is 1mM
The black phosphorus must modified through p-nitrophenyl.
Embodiment 3
Be that black phosphorus nanometer sheet is dissolved in acetonitrile by concentration 500 μ g/ml, drop in surface be coated with by the silicon chip substrate of silicon dioxide from
So it is dried to obtain and is supported on surface and is coated with by the black phosphorus nanometer sheet on the substrate silicon chip of silicon dioxide, then make it at system concentration be
The acetonitrile of the tetra-tert amine hexafluorophosphate of 2.5M and 2,4 dichloro benzene diazonium tetrafluoroborate that system concentration is 100mM is molten
In liquid, lucifuge reaction 24h at 35 DEG C, obtains through 2, the black phosphorus that 4-Dichlorobenzene base is modified.
Embodiment 4
Before carrying out covalent bond with aromatic compound, the most modified black phosphorus stability extreme difference, in atmosphere by
Be oxidized to phosphorus pentoxide, and then and water generate phosphoric acid, produce a large amount of air bubble-shaped forms on black phosphorus surface, and over time
Extending, bubbleization is increasingly severe, and as shown in Fig. 4 a and Fig. 4 b, Fig. 4 a, Fig. 4 b are respectively and expose in atmosphere after 4 days and 7 days
Black phosphorus nanometer sheet exterior view, the most modified black phosphorus bubbleization is serious.
The present embodiment respectively with previous embodiment obtain through p-nitrophenyl modify black phosphorus, repair through p-methoxyphenyl
Decorations black phosphorus and through 2,4 dichloro benzene base modify black phosphorus as a example by observe with aromatic compound carry out covalent bond it
The stability of rear black phosphorus nanometer sheet, the black phosphorus that wherein Fig. 5 a, Fig. 5 b are respectively through p-nitrophenyl modification exposes 4 days in atmosphere
With the exterior view after 7 days；Fig. 6 a, Fig. 6 b are respectively the black phosphorus through modifying methoxybenzene and expose in atmosphere after 4 days and 7 days
Exterior view；Fig. 7 a, Fig. 7 b are respectively through 2, and the black phosphorus that 4-Dichlorobenzene base is modified exposes exterior view after 4 days and 7 days in atmosphere,
The exposure condition of Fig. 5 a～Fig. 7 b exterior view is identical with Fig. 4 a, Fig. 4 b, and observation condition is also identical with Fig. 4 a, Fig. 4 b.
Comparison diagram 4a～4b is from Fig. 5 a～Fig. 7 b it can be seen that after carrying out covalent bond with aromatic compound, black
The stability of phosphorus nanometer sheet is greatly improved, surface no longer bubble, and can the long period stable in the air.
As a example by black phosphorus is modified by the diazol to methoxybenzene, by the observation of atomic force microscope, Ke Yi
Observing stability difference that is the most modified and that pass through the black phosphorus modified in less dimension, as shown in Fig. 8 a, Fig. 8 b, Fig. 8 a is not
7 days rear surface figures placed by modified black phosphorus, and Fig. 8 b is that the black phosphorus through modifying methoxybenzene is under conditions of identical with Fig. 8 a
Place 7 days rear surface figures, comparison diagram 8a and Fig. 8 b it can be seen that 7 days rear surface seriously bubbles placed by the most modified black phosphorus
Change, and the 7 days rear surfaces of black phosphorus placement through modifying methoxybenzene are the most smooth.
As a example by black phosphorus is modified by the diazol to methoxybenzene, by transmission electron microscope (Fig. 9) and high-resolution transmission
Electronic Speculum (Figure 10), can observe and be able to the crystal structure of the black phosphorus that methoxybenzene black phosphorus places 7 days very well after modifying
Holding.
Finally illustrate: above example is merely to illustrate implementation process and the feature of the present invention, and unrestricted is sent out
Bright technical scheme, although being described in detail the present invention with reference to above-described embodiment, those of ordinary skill in the art should
Work as understanding: still the present invention can be modified or equivalent, without departing from the spirit and scope of the present invention any
Amendment or local are replaced, and all should contain in the middle of protection scope of the present invention.
Claims (10)
1. the black phosphorus modified through aromatic compound, the described black phosphorus modified through aromatic compound is black phosphorus and aromatic radical
The product that group is combined by P-C covalent bond.
The most according to claim 1 through aromatic compound modify black phosphorus, wherein, described aromatic group for replace or not
Substituted phenyl；
Preferably, described replacement or the most substituted phenyl have a structure shown in formula (I):
R in formula (I)1～R5It is each independently hydrogen atom, halogen atom, nitro, hydroxyl, C1～6Alkyl, C1～3Alkoxyl；
This C1～6Alkyl be unsubstituted or through one or more following groups replace: halogen atom, nitro, hydroxyl, amino, methyl,
Ethyl, n-pro-pyl；
This C1～3Alkoxyl is unsubstituted or replaces through one or more following groups: halogen atom, nitro, hydroxyl, amino, first
Base, ethyl, n-pro-pyl.
The black phosphorus modified through aromatic compound the most according to claim 2, wherein, described replacement or the most substituted phenyl
There is following structure:
4. according to the black phosphorus modified through aromatic compound according to any one of claims 1 to 3, wherein, described black phosphorus bag
Include black phosphorus alkene, black phosphorus nanometer sheet or black phosphorus crystal, preferably black phosphorus nanometer sheet.
5. the preparation method of the black phosphorus modified through aromatic compound according to any one of Claims 1 to 4, described preparation method
Including making the diazol of aromatic compound and black phosphorus raw material reaction to prepare the described black phosphorus modified through aromatic compound
Step；
Preferably, described black phosphorus raw material is dissolved in organic solvent, adds tetra-tert amine hexafluorophosphate and described aromatic series
The diazol of compound, lucifuge reaction obtains the described black phosphorus modified through aromatic compound；Or
Described black phosphorus raw material is supported in substrate, then makes it containing tetra-tert amine hexafluorophosphate and described aromatic series
In the organic solvent of the diazol of compound, lucifuge reaction obtains the described black phosphorus modified through aromatic compound.
Preparation method the most according to claim 5, wherein, the diazol of described aromatic compound includes aromatic compound
One or more in the diazonium tetrafluoroborate of thing, pyrazoles diazonium inner salt and three dish alkene diazols.
Preparation method the most according to claim 5, wherein, described organic solvent include acetonitrile, ethanol, isopropanol, acetone,
Ethyl acetate, dichloromethane, chloroform, oxolane, N-Methyl pyrrolidone, N,N-dimethylformamide and dimethyl are sub-
One or more in sulfone；
Described substrate includes silicon chip, such as include surface be not coated with by silicon chip, surface be coated with by silicon dioxide or the silicon chip of silicon nitride.
8. according to the preparation method according to any one of claim 5～7, wherein, described black phosphorus raw material is in reaction system
Concentration is 10 μ g/ml～10mg/ml；
Preferably, described tetra-tert amine hexafluorophosphate concentration in reaction system is 0.01～10mol/L；
Preferably, the diazol of described aromatic compound concentration in reaction system is 0.01～100mmol/L；
It is further preferred that described reaction is to react 1～24h at 20～40 DEG C.
9. a compositions, it contains the black phosphorus through aromatic compound modification according to any one of Claims 1 to 4 or power
Profit requires the black phosphorus modified through aromatic compound that the preparation method according to any one of 5～8 prepares.
10. according to any one of Claims 1 to 4 through aromatic compound modify black phosphorus or claim 5～8 in arbitrary
Preparation method described in Xiang prepare through aromatic compound modify black phosphorus or claim 9 described in compositions prepare thin
Film transistor material, the negative material of battery, flexible display material, LED material, optical switch material, biosensor material, light
Application in dynamic therapy reagent or photo-thermal therapy reagent.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104961113A (en) * | 2015-07-01 | 2015-10-07 | 北京石油化工学院 | Method for preparing phosphaalkene |
| WO2016018988A1 (en) * | 2014-07-31 | 2016-02-04 | The University Of North Carolina At Chapel Hill | Two dimensional materials produced by the liquid exfoliation of black phosphorus |
| CN105535971A (en) * | 2015-12-22 | 2016-05-04 | 苏州大学 | A black phosphorus nanometer particle with biocompatibility, a preparing method thereof and applications of the black phosphorus nanometer particle |
-
2016
- 2016-08-23 CN CN201610707744.6A patent/CN106315531B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016018988A1 (en) * | 2014-07-31 | 2016-02-04 | The University Of North Carolina At Chapel Hill | Two dimensional materials produced by the liquid exfoliation of black phosphorus |
| CN104961113A (en) * | 2015-07-01 | 2015-10-07 | 北京石油化工学院 | Method for preparing phosphaalkene |
| CN105535971A (en) * | 2015-12-22 | 2016-05-04 | 苏州大学 | A black phosphorus nanometer particle with biocompatibility, a preparing method thereof and applications of the black phosphorus nanometer particle |
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| CN110917907B (en) * | 2019-12-12 | 2022-03-08 | 万华化学集团股份有限公司 | High-flux reverse osmosis membrane and preparation method and application thereof |
| CN110917907A (en) * | 2019-12-12 | 2020-03-27 | 万华化学集团股份有限公司 | High-flux reverse osmosis membrane and preparation method and application thereof |
| CN111483988A (en) * | 2020-04-17 | 2020-08-04 | 厦门大学 | Preparation method of antioxidant black phosphorus nanosheet |
| CN111646439A (en) * | 2020-06-19 | 2020-09-11 | 昆明理工大学 | Method for doping nano black phosphorus or black phosphorus-based mixed material |
| CN111847408A (en) * | 2020-08-12 | 2020-10-30 | 中国药科大学 | Two-dimensional black phosphorus surface protection method |
| CN111847408B (en) * | 2020-08-12 | 2023-03-24 | 中国药科大学 | Two-dimensional black phosphorus surface protection method |
| CN112110430A (en) * | 2020-09-23 | 2020-12-22 | 中国矿业大学 | Method for improving solubility of black phosphorus of two-dimensional material |
| CN112110430B (en) * | 2020-09-23 | 2021-11-09 | 中国矿业大学 | Method for improving solubility of black phosphorus of two-dimensional material |
| CN112500768A (en) * | 2020-11-27 | 2021-03-16 | 魏刚印 | Water-based antistatic coating and preparation method thereof |
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