CN111646439A - Method for doping nano black phosphorus or black phosphorus-based mixed material - Google Patents
Method for doping nano black phosphorus or black phosphorus-based mixed material Download PDFInfo
- Publication number
- CN111646439A CN111646439A CN202010568734.5A CN202010568734A CN111646439A CN 111646439 A CN111646439 A CN 111646439A CN 202010568734 A CN202010568734 A CN 202010568734A CN 111646439 A CN111646439 A CN 111646439A
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- Prior art keywords
- black phosphorus
- doping
- nano
- nano black
- mixed material
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000000463 material Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000000725 suspension Substances 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000006552 photochemical reaction Methods 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- -1 black phosphorus alkene Chemical class 0.000 claims description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 18
- 229910021389 graphene Inorganic materials 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- 229910052734 helium Inorganic materials 0.000 claims description 5
- 239000001307 helium Substances 0.000 claims description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 5
- 239000002127 nanobelt Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002071 nanotube Substances 0.000 claims description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 239000005388 borosilicate glass Substances 0.000 claims description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052582 BN Inorganic materials 0.000 claims description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims description 2
- 229910052743 krypton Inorganic materials 0.000 claims description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002070 nanowire Substances 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052704 radon Inorganic materials 0.000 claims description 2
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 claims description 2
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910000058 selane Inorganic materials 0.000 claims description 2
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 30
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 238000002360 preparation method Methods 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000004146 energy storage Methods 0.000 abstract description 3
- 230000005669 field effect Effects 0.000 abstract description 3
- 230000004720 fertilization Effects 0.000 abstract description 2
- 239000007921 spray Substances 0.000 abstract description 2
- 239000011521 glass Substances 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 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 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 238000004080 punching Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- WHQOKFZWSDOTQP-UHFFFAOYSA-N 2,3-dihydroxypropyl 4-aminobenzoate Chemical compound NC1=CC=C(C(=O)OCC(O)CO)C=C1 WHQOKFZWSDOTQP-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- MPCRDALPQLDDFX-UHFFFAOYSA-L Magnesium perchlorate Chemical compound [Mg+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O MPCRDALPQLDDFX-UHFFFAOYSA-L 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 206010034962 Photopsia Diseases 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229960005069 calcium Drugs 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 235000011148 calcium chloride Nutrition 0.000 description 2
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 description 2
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 235000019700 dicalcium phosphate Nutrition 0.000 description 2
- SSWAPIFTNSBXIS-UHFFFAOYSA-N dioxido(dioxo)tungsten;iron(2+) Chemical compound [Fe+2].[O-][W]([O-])(=O)=O SSWAPIFTNSBXIS-UHFFFAOYSA-N 0.000 description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 2
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 2
- 230000007613 environmental effect Effects 0.000 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 description 2
- LHOWRPZTCLUDOI-UHFFFAOYSA-K iron(3+);triperchlorate Chemical compound [Fe+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O LHOWRPZTCLUDOI-UHFFFAOYSA-K 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 235000011147 magnesium chloride Nutrition 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- QVRFMRZEAVHYMX-UHFFFAOYSA-L manganese(2+);diperchlorate Chemical compound [Mn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O QVRFMRZEAVHYMX-UHFFFAOYSA-L 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 2
- 235000019691 monocalcium phosphate Nutrition 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229910000065 phosphene Inorganic materials 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 description 2
- 235000011151 potassium sulphates Nutrition 0.000 description 2
- 239000002096 quantum dot Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- MFXMOUUKFMDYLM-UHFFFAOYSA-L zinc;dihydrogen phosphate Chemical compound [Zn+2].OP(O)([O-])=O.OP(O)([O-])=O MFXMOUUKFMDYLM-UHFFFAOYSA-L 0.000 description 2
- JHYNEQNPKGIOQF-UHFFFAOYSA-N 3,4-dihydro-2h-phosphole Chemical compound C1CC=PC1 JHYNEQNPKGIOQF-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- QQFLQYOOQVLGTQ-UHFFFAOYSA-L magnesium;dihydrogen phosphate Chemical compound [Mg+2].OP(O)([O-])=O.OP(O)([O-])=O QQFLQYOOQVLGTQ-UHFFFAOYSA-L 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 229910000401 monomagnesium phosphate Inorganic materials 0.000 description 1
- 235000019785 monomagnesium phosphate Nutrition 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/003—Phosphorus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a method for doping a nano black phosphorus or black phosphorus-based mixed material, which comprises the following steps of firstly, uniformly dispersing the nano black phosphorus or black phosphorus-based mixed material in a solvent or a salt solution to obtain a suspension; secondly, placing the suspension in a glass reactor, continuously introducing doping gas or not introducing doping gas in an inert atmosphere, and then carrying out photochemical reaction under uniform stirring; finally, carrying out solid-liquid separation on the reaction product, and drying the obtained solid, thereby obtaining the doped nano black phosphorus or the doped black phosphorus-based composite material; the method has the characteristics of mild reaction conditions, low cost and large-scale preparation, and the doped nano black phosphorus/black phosphorus-based composite material prepared by the method has practical prospects in the fields of photoelectrons, field effect transistors, energy storage, catalysis, spray fertilization and the like.
Description
Technical Field
The invention relates to a method for doping a nano black phosphorus or black phosphorus-based composite material, belonging to the technical field of nano materials.
Background
The nano black phosphorus is a novel two-dimensional material, and has high carrier mobility, good optical and optoelectronic properties, excellent mechanical properties and the like due to the unique crystal structure and energy band structure, so that the nano black phosphorus has attractive application prospects in the fields of energy storage, field effect transistors, solar cells, gas sensors, biomedicine, catalysis and the like. However, in practical application, the nano black phosphorus has the disadvantages of poor conductivity, poor stability and the like. In order to further promote the application of the nano black phosphorus, the nano black phosphorus is doped with heteroatoms, so that the minimum value of a conduction band of the nano black phosphorus is shifted down to be lower than O2/O2 –The oxidation-reduction potential of the nano black phosphorus increases the structural defects of the nano black phosphorus, changes the electronic characteristics of the nano black phosphorus, thereby improving the electrochemical performance and stability of the nano black phosphorus and widening the application field of the nano black phosphorus. The doping methods adopted at present mainly comprise atomic layer deposition, a ball milling method, a mineralization method, a high-temperature high-pressure method and an electrochemical method, and the composite material prepared by the methods has the defects of uneven doping, high energy consumption, long time consumption, strict equipment requirement, easiness in high-temperature sintering, high cost and the like.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for doping nano black phosphorus or black phosphorus-based mixed material with mild reaction conditions, high efficiency and environmental protection, the method has the characteristics of simplicity, low cost, no expensive and complicated equipment and large-scale production, and the doped material prepared by the method has better application prospect in the fields of photoelectrons, field effect transistors, energy storage, catalysis, spray fertilization and the like due to good conductivity and stability of the doped material.
The method for doping the nano black phosphorus or the black phosphorus-based mixed material comprises the following steps:
(1) uniformly dispersing the nano black phosphorus or black phosphorus-based mixed material in a solvent or a salt solution to obtain a suspension;
the nano black phosphorus is one of black phosphorus quantum dots, black phosphorus nanobelts, black phosphorus alkene, black phosphorus nanotubes, perforated black phosphorus alkene and black phosphorus nanowires; the black phosphorus-based mixed material is a mixture obtained by mixing nano black phosphorus and one or more of graphene, graphene oxide, MXene, boron nitride and transition metal chalcogenide, wherein the nano black phosphorus accounts for 10-90% of the total mass of the black phosphorus-based mixed material;
the concentration of the nano black phosphorus or black phosphorus-based mixed material suspension is 0.1-10 mg/mL;
the solvent is one of water, methanol, ethanol, isopropanol, diethyl ether, cyclohexane, ethylene carbonate, benzene, hydrazine hydrate, acetone, N-methylpyrrolidone, N-dimethylformamide and dimethyl sulfoxide; the salt solution is one or more of sulfate, nitrate, chloride, phosphate, perchlorate, tungstate and tetrafluoroborate solution in any ratio;
wherein the sulfate is one of potassium sulfate, calcium sulfate, magnesium sulfate, zinc sulfate, ferric sulfate, copper sulfate and manganese sulfate; the nitrate is one of potassium nitrate, calcium nitrate, magnesium nitrate, zinc nitrate, ferric nitrate, cupric nitrate and manganese nitrate; the chloride salt is one of potassium chloride, calcium chloride, magnesium chloride, zinc chloride, ferric chloride, cupric chloride, manganese chloride and molybdenum chloride; the phosphate is one of dipotassium hydrogen phosphate, calcium dihydrogen phosphate, calcium hydrogen phosphate, magnesium dihydrogen phosphate, zinc dihydrogen phosphate, copper phosphate, ammonium hydrogen phosphate, diammonium hydrogen phosphate and ammonium dihydrogen phosphate; the perchlorate is one of potassium perchlorate, calcium perchlorate, magnesium perchlorate, ferric perchlorate and manganese perchlorate; the tungstate is one of calcium tungstate, zinc tungstate, ferrous tungstate and ammonium tungstate; the tetrafluoroborate is one of tetrabutyl phosphine tetrafluoroborate, tetrabutyl ammonium tetrafluoroborate, tetraethyl tetrafluoroborate and 1-butyl-3-methylimidazole tetrafluoroborate;
potassium nitrate, potassium sulfate, potassium chloride, dipotassium hydrogen phosphate or potassium perchlorate in the solution are potassium sources; copper sulfate, copper nitrate or copper chloride in the solution is used as a copper source; magnesium sulfate, magnesium nitrate, magnesium chloride, magnesium phosphate or magnesium perchlorate in the solution is used as a magnesium source; calcium nitrate, calcium chloride, calcium sulfate, calcium perchlorate, calcium dihydrogen phosphate or calcium hydrogen phosphate in the solution are used as calcium sources; ferric nitrate, ferric chloride, ferric sulfate, ferric perchlorate or ferrous tungstate in the solution are used as iron sources; manganese nitrate, manganese chloride, manganese sulfate or manganese perchlorate in the solution is taken as a manganese source; molybdenum chloride in the solution or a molybdenum source; zinc nitrate, zinc chloride, zinc sulfate, zinc dihydrogen phosphate or zinc tungstate in the solution are used as zinc sources; the tetrabutyl phosphine tetrafluoroborate, tetrabutyl ammonium tetrafluoroborate, tetraethyl tetrafluoroborate or 1-butyl-3-methylimidazole tetrafluoroborate solution in the solution is taken as a boron source;
(2) placing the suspension liquid obtained in the step (1) in a reactor, continuously introducing doping gas or not introducing doping gas in an inert atmosphere, and then carrying out photochemical reaction for 0.1-72 h under the conditions of stirring and illumination;
the reactor is a quartz glass tube or a high borosilicate glass tube;
the stirring mode is mechanical stirring, airflow stirring or jet stirring;
the inert atmosphere refers to introducing inert gases such as nitrogen, helium, neon, argon, krypton, xenon or radon; the doping gas is one or more of methane, ethylene, ammonia gas, nitric oxide, nitrogen dioxide, sulfur trioxide, hydrogen sulfide, chlorine, hydrogen selenide, boron trichloride and diborane; the doping gas accounts for 5-95% of the total volume of the doping gas and the inert gas;
(3) after the photochemical reaction in the step (2) is finished, carrying out solid-liquid separation on the reaction product, and drying the solid to obtain doped nano black phosphorus or black phosphorus-based mixed material;
the drying mode is one of freeze drying, vacuum drying and natural drying.
The invention has the beneficial effects that:
1. the method adopts a photocatalysis method, has mild reaction conditions, and has the characteristics of simplicity, controllability, no expensive and complicated equipment, environmental protection, low cost and large-scale production;
2. the method can not only improve the doping uniformity of the whole material, but also controllably adjust the doping amount of the whole material through liquid-liquid reaction or liquid-gas reaction;
3. the method adjusts the flow rate of the gas and the concentration of the solution by changing the types of the gas and the salt solution, thereby adjusting the doping source, the doping amount and the doping form;
4. the doped nano black phosphorus or doped black phosphorus-based composite material prepared by the method has good stability and can be better applied to various fields.
Drawings
FIG. 1 is a spectrum diagram of N1S of a nitrogen-doped perforated black phosphorus alkene/reduced graphene oxide composite material prepared in example 1 of the present invention;
fig. 2 is a fourier transform infrared spectrum of a composite material of the nitrogen-doped perforated black phosphorus alkene/reduced graphene oxide composite material prepared in example 1 of the present invention and a single graphene oxide (in the absence of perforated black phosphorus alkene);
FIG. 3 is a graph of the UV-vis absorption spectrum of (a) a single perforated black phospholene dispersion prepared in example 1 of the present invention; (b) a UV-vis absorption spectrogram of the nitrogen-doped perforated black phosphorus alkene/reduced graphene oxide composite material;
fig. 4 is a constant current charge-discharge curve of the nitrogen-doped perforated black phosphorus alkene/reduced graphene oxide composite material applied to the negative electrode material of the sodium ion battery, which is prepared in embodiment 1 of the invention.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the invention is not limited to the above-described examples.
Example 1: the preparation method of the nitrogen-doped perforated black phosphorus alkene/reduced graphene oxide (N-HBP/rGO) composite material comprises the following steps:
(1) uniformly dispersing 250mg of perforated black phosphorus alkene and 50mg of graphene oxide in 60mL of ethanol to obtain a suspension;
(2) placing the suspension obtained in the step (1) in a quartz glass tube, continuously introducing argon and ammonia (the ammonia accounts for 50% of the total gas amount), and then carrying out ultraviolet irradiation reaction under the magnetic stirring of 300 r/min;
(3) after the ultraviolet light irradiation reaction in the step (2) is carried out for 72 hours, carrying out solid-liquid separation on the reaction product, and carrying out freeze drying on the obtained solid to prepare the N-HBP/rGO composite material;
fig. 1 is a N1S spectrogram of the nitrogen-doped perforated black phosphorus alkene/reduced graphene oxide composite material prepared in the embodiment, and it can be seen from the chart that P-N and C-N bonds in the N-HBP/rGO composite material prepared by the method can prove that nitrogen atoms are successfully doped into the composite material through a photocatalytic reaction, which is expected to improve the stability of the composite material, and this conclusion can be confirmed by a subsequent UV-vis absorption spectrogram;
FIG. 2 is a Fourier transform infrared spectrogram of the nitrogen-doped perforated black phosphorus/reduced graphene oxide composite material prepared in the present example and single graphene oxide (without black phosphorus), and it can be known that the infrared spectrogram of the N-HBP/rGO composite material prepared by the method of the present invention is 1170 cm-1And 920cm-1Two new peaks appear, which can be attributed to the peaks of the P-N and C-N bonds, together with the above-mentioned N1SThe results of the spectrum conjectures are consistent;
fig. 3 is a UV-vis absorption spectrum of the nitrogen-doped perforated black phosphorus alkene/reduced graphene oxide composite material prepared in this example, in order to evaluate the stability of the N-HBP/rGO composite material, the N-HBP/rGO composite material is prepared into an aqueous dispersion, wherein the content of the perforated black phosphorus alkene is 1 mg/mL; for comparison, a single perforated black phosphorus alkene is also prepared into a 1mg/mL aqueous dispersion, the dispersion is directly exposed to the air, samples are taken at different time points respectively to carry out UV-vis absorption spectrogram tests, and the test results are shown in FIGS. 3 (a) (b); with the prolonging of the exposure time, the ultraviolet absorption intensity of the single punching black phosphorus alkene is obviously reduced, which indicates that the punching black phosphorus alkene is continuously oxidized and decomposed; in contrast, the ultraviolet absorption intensity of the N-HBP/rGO composite material has no obvious change, and the comparison shows that the stability of the perforated black phosphene in the N-HBP/rGO composite material is obviously improved;
fig. 4 is a constant current charging and discharging curve of the nitrogen-doped perforated black phosphorus alkene/reduced graphene oxide composite material applied to the negative electrode material of the sodium ion battery, and compared with single black phosphorus, the cycle performance of the nitrogen-doped perforated black phosphorus alkene/reduced graphene oxide composite material is remarkably improved.
Example 2: the preparation method of the sulfur-doped black phosphorus quantum dot comprises the following steps:
(1) uniformly dispersing 300mg of black phosphorus quantum dots in 30mL of N-methylpyrrolidone solvent to obtain a suspension;
(2) placing the suspension obtained in the step (1) in a high borosilicate glass tube, continuously introducing helium and hydrogen sulfide (helium accounts for 35% of the total gas amount), and then carrying out visible light irradiation reaction under the condition of gas flow stirring;
(3) and (3) after the visible light irradiation reaction in the step (2) is carried out for 48 hours, finally, carrying out solid-liquid separation on the reaction product, and carrying out vacuum drying on the obtained solid to obtain the sulfur-doped black phosphorus quantum dot material.
Example 3: the preparation method of the carbon and nitrogen double-doped black phosphorus nanobelt/graphene composite material comprises the following steps:
(1) uniformly dispersing 150mg of black phosphorus nanobelt and 150mg of MXene in 300mL of dimethyl sulfoxide solvent to obtain a suspension;
(2) placing the suspension obtained in the step (1) in a quartz glass tube, continuously introducing nitrogen, ethylene and ammonia (the ethylene and the ammonia account for 60% of the total volume of the gas, and the volume ratio of the ethylene to the ammonia is 1: 1), and then carrying out ultraviolet irradiation reaction under jet stirring;
(3) and (3) after the ultraviolet light irradiation reaction in the step (2) is carried out for 2 hours, finally, carrying out solid-liquid separation on the reaction product, and naturally drying the obtained solid to obtain the carbon and nitrogen double-doped black phosphorus nanobelt/MXene composite material.
Example 4: the preparation method of the potassium-doped black phosphorus nanotube composite material comprises the following steps:
(1) uniformly dispersing 300mg of black phosphorus nano-particles in 60mL of 2mol/L potassium chloride solution to obtain a suspension;
(2) placing the suspension obtained in the step (1) in a quartz glass tube, continuously introducing argon, and then carrying out ultraviolet irradiation reaction under the condition of uniform jet stirring;
(3) and (3) after the ultraviolet light irradiation reaction in the step (2) is carried out for 72 hours, finally, carrying out solid-liquid separation on the reaction product, and freeze-drying the obtained solid to obtain the potassium-doped black phosphorus nanotube material.
Example 5: the iron-doped black phosphorus alkene/metal sulfur group compound (MoS)2) The preparation method of the composite material comprises the following steps:
(1) 50mg of black phosphene are reacted with 250mg of transition metal chalcogenide (MoS)2) Uniformly dispersing the mixture in 60mL of 1.5mol/L ferric chloride solution to obtain suspension;
(2) placing the suspension obtained in the step (1) in a quartz tube, continuously introducing helium, and then carrying out visible light irradiation reaction under the condition of uniform-speed airflow stirring;
(3) after the visible light irradiation reaction in the step (2) is carried out for 48 hours, finally, the solid-liquid separation is carried out on the reaction product, the obtained solid is dried in vacuum, and the iron-doped black phosphorus alkene/metal sulfur group compound (MoS) is obtained2) A composite material.
Example 6: the preparation method of the iron and copper double-doped punching black phosphorus alkene material comprises the following steps:
(1) uniformly dispersing 300mg of perforated black phosphorus in 30mL of 2mol/L ferric chloride solution and 30mL of 2mol/L copper chloride solution to obtain suspension;
(2) placing the suspension obtained in the step (1) in a quartz tube, continuously introducing nitrogen, and then carrying out ultraviolet irradiation reaction under uniform mechanical stirring;
(3) and (3) after the ultraviolet light irradiation reaction in the step (2) is carried out for 2 hours, finally, carrying out solid-liquid separation on the reaction product, and carrying out vacuum drying on the obtained solid to obtain the iron and copper double-doped punching black phosphorus alkene material.
While the present invention has been described in detail with reference to the specific embodiments thereof, the present invention is not limited to the embodiments described above, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (9)
1. A method for doping nano black phosphorus or black phosphorus-based mixed materials is characterized by comprising the following specific steps:
(1) uniformly dispersing the nano black phosphorus or black phosphorus-based mixed material in a solvent or a salt solution to obtain a suspension;
(2) placing the suspension liquid obtained in the step (1) in a reactor, continuously introducing doping gas or not introducing doping gas in an inert atmosphere, and then carrying out photochemical reaction under the conditions of stirring and illumination;
(3) and (3) after the photochemical reaction in the step (2) is finished, carrying out solid-liquid separation on the reaction product, and drying the solid to obtain the doped nano black phosphorus or black phosphorus-based mixed material.
2. The method of doping nano black phosphorus or black phosphorus based hybrid material as claimed in claim 1, wherein: the nano black phosphorus is one of black phosphorus quantum dots, black phosphorus nanobelts, black phosphorus alkene, black phosphorus nanotubes, perforated black phosphorus alkene and black phosphorus nanowires; the black phosphorus-based mixed material is a mixture obtained by mixing nano black phosphorus and one or more of graphene, graphene oxide, MXene, boron nitride and transition metal chalcogenide, wherein the nano black phosphorus accounts for 10-90% of the total mass of the black phosphorus-based mixed material.
3. The method of doping nano black phosphorus or black phosphorus based hybrid material as claimed in claim 1, wherein: the concentration of the suspension of the nano black phosphorus or black phosphorus-based mixed material in the step (1) is 0.1-10 mg/mL.
4. The method of doping nano black phosphorus or black phosphorus based hybrid material as claimed in claim 1, wherein: the solvent in the step (1) is one of water, methanol, ethanol, isopropanol, diethyl ether, cyclohexane, ethylene carbonate, benzene, hydrazine hydrate, acetone, N-methylpyrrolidone, N-dimethylformamide and dimethyl sulfoxide; the salt solution is one or more of sulfate, nitrate, chloride, phosphate, perchlorate, tungstate and tetrafluoroborate solution.
5. The method of doping nano black phosphorus or black phosphorus based hybrid material as claimed in claim 1, wherein: the reactor in the step (1) is a quartz glass tube or a high borosilicate glass tube.
6. The method of doping nano black phosphorus or black phosphorus based hybrid material as claimed in claim 1, wherein: the stirring mode in the step (2) is mechanical stirring, airflow stirring or jet stirring.
7. The method of doping nano black phosphorus or black phosphorus based hybrid material as claimed in claim 1, wherein: the inert atmosphere is introduced with inert gases of nitrogen, helium, neon, argon, krypton, xenon or radon; the doping gas is one or more of methane, ethylene, ammonia gas, nitric oxide, nitrogen dioxide, sulfur trioxide, hydrogen sulfide, chlorine, hydrogen selenide, boron trichloride and diborane.
8. The method of doping nano black phosphorus or black phosphorus based hybrid material as claimed in claim 7, wherein: the doping gas accounts for 5-95% of the total volume of the doping gas and the inert gas.
9. The method of doping nano black phosphorus or black phosphorus based hybrid material as claimed in claim 1, wherein: the photochemical reaction time is 0.1-72 h.
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