CN103183342B - Controllable synthetic method for phosphorus doped graphitization carbon spheres with hollow structures - Google Patents
Controllable synthetic method for phosphorus doped graphitization carbon spheres with hollow structures Download PDFInfo
- Publication number
- CN103183342B CN103183342B CN201310114192.4A CN201310114192A CN103183342B CN 103183342 B CN103183342 B CN 103183342B CN 201310114192 A CN201310114192 A CN 201310114192A CN 103183342 B CN103183342 B CN 103183342B
- Authority
- CN
- China
- Prior art keywords
- salt
- high temperature
- carbon
- ratio
- nanometers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 105
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 58
- 239000011574 phosphorus Substances 0.000 title claims abstract description 58
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000005087 graphitization Methods 0.000 title claims abstract description 13
- 238000010189 synthetic method Methods 0.000 title abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 230000009467 reduction Effects 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 239000000047 product Substances 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 239000003929 acidic solution Substances 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 238000002791 soaking Methods 0.000 claims abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 84
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 70
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 50
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 42
- 239000008367 deionised water Substances 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 39
- 229910052742 iron Inorganic materials 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 238000001291 vacuum drying Methods 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 15
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 15
- 239000008103 glucose Substances 0.000 claims description 15
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 claims description 14
- 229940079864 sodium stannate Drugs 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 239000001307 helium Substances 0.000 claims description 9
- 229910052734 helium Inorganic materials 0.000 claims description 9
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 238000005554 pickling Methods 0.000 claims description 7
- -1 polyoxyethylene Polymers 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000001308 synthesis method Methods 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 5
- 229930006000 Sucrose Natural products 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- 239000003637 basic solution Substances 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 claims description 4
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- IOUCSUBTZWXKTA-UHFFFAOYSA-N dipotassium;dioxido(oxo)tin Chemical compound [K+].[K+].[O-][Sn]([O-])=O IOUCSUBTZWXKTA-UHFFFAOYSA-N 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 3
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 3
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims description 3
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- BYGOPQKDHGXNCD-UHFFFAOYSA-N tripotassium;iron(3+);hexacyanide Chemical compound [K+].[K+].[K+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] BYGOPQKDHGXNCD-UHFFFAOYSA-N 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 240000003936 Plumbago auriculata Species 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 241000220317 Rosa Species 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- FRHBOQMZUOWXQL-UHFFFAOYSA-L ammonium ferric citrate Chemical compound [NH4+].[Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FRHBOQMZUOWXQL-UHFFFAOYSA-L 0.000 claims description 2
- DAPUDVOJPZKTSI-UHFFFAOYSA-L ammonium nickel sulfate Chemical compound [NH4+].[NH4+].[Ni+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DAPUDVOJPZKTSI-UHFFFAOYSA-L 0.000 claims description 2
- 239000011260 aqueous acid Substances 0.000 claims description 2
- 239000011449 brick Substances 0.000 claims description 2
- 239000011797 cavity material Substances 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 239000010431 corundum Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- NUHXWPRATKOXDB-UHFFFAOYSA-L diazanium;cobalt(2+);disulfate Chemical compound [NH4+].[NH4+].[Co+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O NUHXWPRATKOXDB-UHFFFAOYSA-L 0.000 claims description 2
- 229960004642 ferric ammonium citrate Drugs 0.000 claims description 2
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000004313 iron ammonium citrate Substances 0.000 claims description 2
- 235000000011 iron ammonium citrate Nutrition 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- UETZVSHORCDDTH-UHFFFAOYSA-N iron(2+);hexacyanide Chemical compound [Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] UETZVSHORCDDTH-UHFFFAOYSA-N 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LVIYYTJTOKJJOC-UHFFFAOYSA-N nickel phthalocyanine Chemical compound [Ni+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 LVIYYTJTOKJJOC-UHFFFAOYSA-N 0.000 claims description 2
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 claims description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical compound [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 claims description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 2
- DITXJPASYXFQAS-UHFFFAOYSA-N nickel;sulfamic acid Chemical compound [Ni].NS(O)(=O)=O DITXJPASYXFQAS-UHFFFAOYSA-N 0.000 claims description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- GTSHREYGKSITGK-UHFFFAOYSA-N sodium ferrocyanide Chemical compound [Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] GTSHREYGKSITGK-UHFFFAOYSA-N 0.000 claims description 2
- 235000012247 sodium ferrocyanide Nutrition 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 claims description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 abstract description 21
- 239000000463 material Substances 0.000 abstract description 15
- 238000002360 preparation method Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000004146 energy storage Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 description 40
- 230000008569 process Effects 0.000 description 29
- 239000011148 porous material Substances 0.000 description 21
- 239000012535 impurity Substances 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 6
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 4
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 239000002609 medium Substances 0.000 description 4
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 239000011796 hollow space material Substances 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002091 nanocage Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- BSWWXRFVMJHFBN-UHFFFAOYSA-N 2,4,6-tribromophenol Chemical compound OC1=C(Br)C=C(Br)C=C1Br BSWWXRFVMJHFBN-UHFFFAOYSA-N 0.000 description 1
- 239000000592 Artificial Cell Substances 0.000 description 1
- 241000143432 Daldinia concentrica Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical group O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000004411 aluminium Substances 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
- 230000009286 beneficial effect Effects 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical class OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229940045641 monobasic sodium phosphate Drugs 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 238000002910 structure generation Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical class [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
Abstract
A controllable synthetic method for phosphorus doped graphitization carbon spheres with hollow structures comprises the following preparation steps: (1), dissolving silicon source, soluble metal salt and catalyst into resolvent according to molar ratio, stirring until complete resolution and then transferring to a hydrothermal reaction kettle for hydro-thermal synthesis, then cleaning, filtering and drying the obtained precipitate so as to obtain a primary commodity;(2), reducing the obtained primary commodity in a high-temperature reaction furnace under gas shield at high temperature;(3), placing the product obtained through high temperature reduction into acidic solution for soaking, cleaning, filtering and drying, finally, for phosphorus doped graphitization carbon spheres with hollow structures can be obtained. According to the invention, the phosphorus doped graphitization carbon spheres with hollow structures have the advantages that the appearances are uniform, a carbon shell is provided with a micropore structure, mesoporous carbon support structures are arranged inside the carbon spheres, the graphitization degree is excellent, and the phosphorus doped graphitization carbon spheres can be used in numerous fields of efficient catalysis and conversion, energy storage and conversion, medicine release and control, material adsorption stripping and the like. The template-free hydro-thermal synthesis technology is simple and controllable, and can be used for mass production.
Description
Technical field
The synthetic method that the present invention relates to a kind of phosphorus doping nano hollow carbon ball, particularly a kind of phosphorus doping has the controllable synthesis method of hollow structure graphitized carbon ball.
Background technology
Nano hollow carbon ball is a kind of special carbon material, there is high chemical stability, lower density, good thermostability and biocompatibility, not only can be used as electrode materials, support of the catalyst, gas storage medium, lubricant, material fractionation by adsorption, drug sensor, drugrelease, artificial cell, prepare the template of other materials etc., also, as various fields such as dyestuff, rubber reinforcement material, lightweight structural materials, attracted increasing concern.
Hollow carbon sphere is mainly prepared by methods such as organism Pintsch process, chemical vapour deposition, medium reduction, laser distillation, arc-over, template self-assemblies at present.These methods will be carried out conventionally under hot conditions, long reaction time, and energy consumption is large, and not only apparatus expensive, complicated operation, cost are higher, and hollow ball shape irregularity productive rate low-purity is not high, has directly affected suitability for industrialized production and the application thereof of hollow carbon sphere.Therefore explore the technology that low temperature is prepared hollow carbon sphere on a large scale, not only contribute to inquire into theoretically the formation mechanism of hollow carbon sphere, and supply raw materials for its performance of research, contribute to promote the widespread use of hollow ball.
The synthetic method of hollow carbon sphere generally speaking can be concluded and be divided into two classes, template and without template, and wherein template is most widely used general.Its advantage is that pore passage structure and pattern are controlled, can design the hollow material of synthetic different size and pattern by adjusting the size and shape of template.It is template that aluminium meso-porous silica core-shell structure ball is mixed in ZL200910055527.3 employing, and furfuryl alcohol is carbon source, by removing template silicon-dioxide after its polymerization, carbonization, has prepared small-size meso-porous hollow carbon sphere.ZL200910198399.8 provides a kind of vacuum nano to build the method for preparing magnetic kernel medium hole hollow carbon sphere, take mesoporous SiO 2 hollow ball as basis, by the air pressure inside and outside change hollow ball, the source of iron solution of different concns is injected in hollow core, after thermal treatment, furfuryl alcohol is poured on hollow ball, by utilizing sodium hydroxide solution to remove silica template after its polymerization, carbonization, obtain having the meso-porous hollow carbon sphere of magnetic kernel.In whole preparation process, first to synthesize template and then will remove material that template is finally synthesized containing template.This has just caused three problems, and one is to synthesize and remove template to cause the manufacture process of whole material loaded down with trivial details, is unfavorable for that large-scale material is synthetic, has increased cost; Another problem is that hollow material output is lower; The 3rd, last in removing the process of template, if the strength of materials covering is not enough, may cause structural collapse to cause material to synthesize unsuccessfully.
For these shortcomings of template, people explore without template and synthesize hollow carbon material.
ZL200410024700.0, adopts chemical Vapor deposition process to prepare the nano cages with hollow structure ZL200610027992.2 and ZL200510110213.0 mix metal carbonyls liquid with low-carbon (LC) class organic liquid after.Magnesiumcarbonate be take as catalyzer in Nanjing University's (application number 201210062927.9), adopts chemical Vapor deposition process to prepare the hollow nano cages of nitrogen doping.Although chemical Vapor deposition process operates fairly simple, synthetic material shape irregularity, these materials in use tend to show the unstable of structure and the unhomogeneity of performance.Oxygen-bearing organic matter is usingd as carbon source in Shandong University's (application number 200810015929.6), packs reactor into, 500 ~ 600 with metallic zinc after mixing
oc reaction 4 ~ 8 hours obtains nano hollow carbon ball after pickling.Owing to adopting metallic zinc as catalyzer and template, the internal diameter variable range of hollow ball is very little.Heilongjiang University's (application number 201210128545.1) adopts after trimeric cyanamide powder and formaldehyde solution Hydrothermal Synthesis the method for Pintsch process again to prepare nitrogenous greying hollow carbon sphere, and trimeric cyanamide wherein had not only served as template but also as carbon source.Although this method need not be added template and catalyzer in synthetic process, due to the limitation of trimeric cyanamide powder itself, limited equally the internal diameter of this hollow carbon sphere.ZL200910111112.3 is dissolved in source of iron in lower alcohol, and mix with the toluene solution containing tribromophenol or chlorophenesic acid, add afterwards the thermal synthesis of nitrogenous source high-temperature water to obtain the hollow Nano carbon balls of hydroxyl and amino functional, but because the later stage lacks pyroprocessing, be difficult to obtain graphited hollow carbon sphere.South China Science & Engineering University's (application number 201010528639.9) is dissolved in triphenylphosphine in toluene, adopt chemical Vapor deposition process to make phosphorus-doped spherical graphite, although do not add any catalyzer, resulting graphite pebbles pattern can not evenly be controlled and be not hollow structure.
The hot method of solvent (water) is synthetic the have compound of special construction and performance and the effective ways of novel material.Adopt water or organic solvent as reaction medium, mixing raw material reacts, and obtains carbon material after high temperature cabonization.(the Nano-architectures of ordered hollow carbon spheres filled with carbon webs by template-free controllable synthesis such as Hu Zhuofeng, Zhuofeng Hu, et al. Nanotechnology, 2012
23(48): 1-10.) take glucose and sodium stannate as raw material, Hydrothermal Synthesis the adjustable hollow carbon sphere of structure.But the carbon ball that this synthetic method obtains does not have graphite carbon to be existed.
Summary of the invention
It is simple that the object of the invention is to provide a kind of technique, with low cost, and the phosphorus doping that product purity is high has the controllable synthesis method of hollow structure graphitized carbon ball.
The object of the present invention is achieved like this, this controllable synthesis method, and step is:
(1) hydro-thermal is prepared nucleocapsid structure carbon ball
Carbon source, soluble metallic salt, catalyzer are dissolved in solvent according to mol ratio, are stirred to completely and are transferred to hydrothermal reaction kettle Hydrothermal Synthesis after dissolving, by the sediment undergoes washing obtaining, filtration, dry, obtain primary products;
(2) high temperature reduction of carbon ball
In high temperature reaction stove by the primary products that obtain high temperature reduction under gas shield;
(3) prepare hollow plumbago carbon ball
The product that high temperature reduction is obtained is placed in after acidic solution immersion, cleans, filters, is dried, and obtains the graphitized carbon ball that phosphorus doping has hollow structure;
Carbon source in step (1) is for being wherein any one of glucose, sucrose, starch, polyvinyl alcohol, polyoxyethylene glycol, polystyrene, phenol, Resorcinol, toluene, PAPE, diethylene triamine pentamethylene phosphonic or HMPA;
Solvent in step (1) is wherein any one of deionized water, polyphosphoric acid or the phosphorous aqueous solution;
Soluble metallic salt in step (1) is stanniferous metal-salt or the metal-salt that contains zinc, dissolves in 20 ~ 100
othe pure water of C or acidity or basic solution; Wherein stanniferous metal-salt is wherein any one of sodium stannate, potassium stannate, stannous sulfate, stannous oxalate, tindichloride or tin tetrachloride; Containing the metal-salt of zinc, be wherein any one of zinc acetate, zinc iodide, zinc fluoride, zinc chloride, zinc sulfate, zinc phosphate or zinc nitrate;
The metal-salt that described catalyzer in step (1) is iron content or containing the metal-salt of cobalt or nickeliferous metal-salt, dissolves in 20 ~ 100
othe pure water of C or acidity or basic solution; The metal-salt of described iron content is wherein any one of iron(ic) chloride, ferric sulfate, iron nitrate, the Tripotassium iron hexacyanide, yellow prussiate of potash, yellow prussiate of soda, ferrous sulfate, iron protochloride, ferrous ammonium sulphate, ironic acetate, ferric fluoride, ferric ammonium citrate, ironic citrate or Hexacyanoferrate potassium; The described metal-salt containing cobalt is wherein any one of Cobaltous diacetate, rose vitriol, cobalt chloride, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, ammonium cobaltous sulfate or sodium cobaltinitrite; Nickeliferous metal-salt is wherein any one of nickelous bromide, nickelous acetate, single nickel salt, nickelous chloride, nickel ammonium sulfate, nickelous nitrate, nickel sulfamic acid, nickelous fluoride or nickelous carbonate;
The proportioning of the carbon source in step (1), soluble metallic salt, catalyzer is mol ratio 5 ~ 300:1:0.1 ~ 50; In the situation that carbon source content is certain, can regulate by adjusting the ratio of soluble metallic salt the inner/outer diameter ratio of hollow ball, by regulating the ratio of catalyzer and the degree of graphitization that high temperature reduction temperature is adjusted final product;
Hydrothermal Synthesis temperature in step (1) is 100 ~ 300
oc, 2 ~ 36 hours Hydrothermal Synthesis time;
In step (1) and step (3), for the reagent cleaning, be acetone or alcohol or 20 ~ 100
othe deionized water of C, purging method is for filtration or centrifugal, 60 ~ 300
ounder C vacuum-drying or protection of inert gas, be dried 1 ~ 24 hour; Wherein rare gas element is a kind of or its mixture in nitrogen, argon gas, helium, and proportioning is any, and wherein the purity of nitrogen, argon gas, helium is more than or equal to 99.99%;
Gas in step (2) is a kind of or its mixture in nitrogen, argon gas, helium, hydrogen, and proportioning is any, and wherein the purity of nitrogen, argon gas, helium, hydrogen is more than or equal to 99.99%, and gas flow is 5 ~ 500 ml/min;
High temperature reaction stove in step (2) can time variable control heats up, and can pass into gas shield, adopts air-cooled or recirculated water or shallow-layer refrigerated water cooling; Sample is placed in to the middle section of high temperature reaction stove, High Temperature Furnaces Heating Apparatus can be retort furnace, tube furnace or microwave oven, and cavity material can be quartz, corundum, pottery, stainless steel or insulating brick;
In step (2), the temperature of high temperature reduction is 500 ~ 3200
oc, the recovery time is 0.1 ~ 36 hour, heat-up rate is per minute 0.1 ~ 50
oc;
Acidic solution is acid iodide, Periodic acid, phosphoric acid, strong inorganic acid and mixing aqueous acid thereof in step (3), guarantees that pH is less than under 7 prerequisite to mix with arbitrary proportion; When carbon source and solvent are all not phosphorous, in the reagent of pickling, must have a kind of acid is phosphoric acid or the mixed solution that contains phosphoric acid, and wherein the ratio of phosphoric acid is any and non-vanishing;
The product first high temperature reduction being obtained before soaking in step (3) and acidic solution are ultrasonic or be uniformly mixed to being uniformly dispersed 20 ~ 200
oin C temperature range, soak 0.1 ~ 48 hour, then mixed solution is diluted to cleaning and filtering, and filtrate recycling recycling.
Beneficial effect, owing to having adopted such scheme, the preparation method of this phosphorus doping hollow structure graphitized carbon ball, products obtained therefrom purity is high, substantially free from foreign meter, pattern is even, carbon shell has microvoid structure, carbon ball inside has mesoporous carbon supporting structure, degree of graphitization is good.By regulating the ratio of carbon source and soluble metallic salt or the ratio that kind is controlled the inner/outer diameter of hollow carbon sphere, and micropore and mesoporous ratio.By adjusting ratio and the high temperature reduction temperature of catalyzer, control degree of graphitization.By the content of phosphorus or the concentration of hydrothermal temperature or hydro-thermal time or pickling temperature or pickling time or phosphoric acid solution in adjusting carbon source kind or Hydrothermal Synthesis, control the content of phosphorus.Soluble metallic salt and catalyzer as presoma are cheap, and easily recycling, can reduce costs environmental protection.Hollow structure graphitized carbon ball has and the diverse characteristic of conventional graphite material, can be used as catalytic material transforms for efficient catalytic, as electrode materials, be used for energy storage and conversion, as pharmaceutical carrier, be used for drugrelease, as gas storage medium, be used for storing up hydrogen separated with gas trapping, as filtering adsorbing material for separating substances, as template for the preparation of other nano materials, as conductive agent, as electrode materials, as lightweight strongthener, be used for the various fields such as rubber and resin enhancing.
Advantage: technique is simple, with low cost, product purity is high, the phosphorus doping hollow structure graphitized carbon ball making have pattern evenly, carbon shell has microvoid structure, carbon ball inside and has mesoporous carbon supporting structure, degree of graphitization is good, can be used for the various fields such as efficient catalytic conversion, energy storage and conversion, drugrelease, material fractionation by adsorption, atmosphere storage.
Embodiment
Below by embodiment in detail the present invention is described in detail.
embodiment 1:first by 4.0 grams of glucose, 0.21 gram of sodium stannate, 0.22 gram of iron(ic) chloride, mol ratio 25:1:1, is dissolved in 40 ml deionized water, moves into the hydrothermal reaction kettle of 50 milliliters, 160 after stirring
oc reaction after 15 hours is filtered reaction product, with 25
oc washed with de-ionized water is removed impurity.By reaction product 70
oafter C vacuum-drying 12 hours, then be placed in high temperature process furnances 1000
oc heating 2 hours, heat-up rate 5
oc per minute, 30 milliliters of per minutes of nitrogen flow, naturally cool to after room temperature, by 14 mol/L phosphatase 79s 0
oc soaks 6 hours except detin and iron, obtain the graphitized carbon ball that phosphorus doping has hollow structure, its external diameter 224 nanometers, internal diameter 140 nanometers, the ratio of external diameter/internal diameter is 1.6, carbon shell pore size (0.7 nanometer, 1.1 nanometers), mesoporous size 4.7 nanometers of carbon core, approximately 420 square metres every gram of specific surface area, greying ratio is 98.9%, and phosphorus content is 1.7%.
The soluble metallic salt adding is stanniferous metal-salt or the metal-salt that contains zinc, and the fusing point of this two classes salt is very low, during heat, easily from carbon shell, flows out, and forms and has mesoporous hollow carbon.
Adding catalyzer is in order to reduce graphitization temperature, to reach the object that reduces energy consumption.
In the situation that carbon source content is certain, can regulate by adjusting the ratio of soluble metallic salt the inner/outer diameter ratio of hollow ball, by regulating the ratio of catalyzer and the degree of graphitization that high temperature reduction temperature is adjusted final product.
By the content of phosphorus or the concentration of hydrothermal temperature or hydro-thermal time or pickling temperature or pickling time or phosphoric acid solution in adjusting carbon source kind or Hydrothermal Synthesis, control the content of phosphorus.
Control heat-up rate well, heat-up rate is too fast can not obtain the structure of wishing, heat-up rate is crossed slowly can cause energy dissipation.
The acidic solution adopting can not be to graphitized carbon material structure generation destruction, therefore concentration limit not, but had better not use strong solution, but concentration can not be too low, otherwise can cause removal efficiency decline.
embodiment 2:first by 4.0 grams of glucose, 0.21 gram of sodium stannate, 0.22 gram of iron(ic) chloride, mol ratio 25:1:1, is dissolved in the deionized water of 20 milliliters and the mixed solution of 20 milliliters of phosphoric acid (phosphoric acid concentration 52% ~ 54%), moves into the hydrothermal reaction kettle of 50 milliliters, 160 after stirring
oc reaction after 3 hours is filtered reaction product, with 25
oc washed with de-ionized water is removed impurity.By reaction product 100
oafter C vacuum-drying 4 hours, then be placed in high temperature process furnances 1000
oc heating 2 hours, heat-up rate 5
oc per minute, 30 milliliters of per minutes of nitrogen flow, naturally cool to after room temperature, by 5 mol/L phosphatase 79s 0
oc soaks 6 hours except detin and iron, obtain the graphitized carbon ball that phosphorus doping has hollow structure, its external diameter 94 nanometers, internal diameter 71 nanometers, the ratio of external diameter/internal diameter is 1.3, carbon shell pore size (0.7 nanometer, 1.1 nanometers), mesoporous size 4.7 nanometers of carbon core, approximately 521 square metres every gram of specific surface area, greying ratio is 97.8%, and phosphorus content is 7.2%.
embodiment 3:first by 4.0 grams of glucose, 0.21 gram of sodium stannate, 0.22 gram of iron(ic) chloride, mol ratio 25:1:1, is dissolved in the deionized water of 10 milliliters and the mixed solution of 30 milliliters of phosphoric acid (phosphoric acid concentration 52% ~ 54%), moves into the hydrothermal reaction kettle of 50 milliliters, 160 after stirring
oc reaction after 9 hours is filtered reaction product, with 50
oc washed with de-ionized water is removed impurity.By reaction product 100
oafter C vacuum-drying 4 hours, then be placed in high temperature process furnances 1000
oc heating 2 hours, heat-up rate 5
oc per minute, 30 milliliters of per minutes of nitrogen flow, naturally cool to after room temperature, by 2 mol/L phosphatase 79s 0
oc soaks 6 hours except detin and iron, obtain the graphitized carbon ball that phosphorus doping has hollow structure, its external diameter 125 nanometers, internal diameter 104 nanometers, the ratio of external diameter/internal diameter is 1.2, carbon shell pore size (0.7 nanometer, 1.1 nanometers), mesoporous size 4.7 nanometers of carbon core, approximately 530 square metres every gram of specific surface area, greying ratio is 98.7%, and phosphorus content is 6.9%.
embodiment 4:first by 4.0 grams of glucose, 1.07 grams of sodium stannates, 1.08 grams of iron(ic) chloride, mol ratio 5:1:1, is dissolved in 40 milliliters containing the aqueous solution of 10 grams of sodium phosphates, moves into the hydrothermal reaction kettle of 50 milliliters, 160 after stirring
oc reaction after 15 hours is filtered reaction product, with 25
oc washed with de-ionized water is removed impurity.By reaction product 150
oafter C vacuum-drying 2 hours, then be placed in high temperature process furnances 700
oc heating 2 hours, heat-up rate 5
oc per minute, 30 milliliters of per minutes of nitrogen flow, naturally cool to after room temperature, by 1 mol/L sulfuric acid 75
oc soaks 12 hours except detin and iron, obtain the graphitized carbon ball that phosphorus doping has hollow structure, its external diameter 123 nanometers, internal diameter 115 nanometers, the ratio of external diameter/internal diameter is 1.1, carbon shell pore size (0.7 nanometer, 1.1 nanometers), mesoporous size 4.7 nanometers of carbon core, approximately 572 square metres every gram of specific surface area, greying ratio is 99.8%, and phosphorus content is 7.3%.
embodiment 5:first by 8.0 grams of glucose, 0.24 gram of sodium stannate, 0.24 gram of iron(ic) chloride mol ratio 50:1:1, be dissolved in the deionized water of 10 milliliters and the mixed solution of 30 milliliters of phosphoric acid (phosphoric acid concentration 52% ~ 54%), after stirring, move into the hydrothermal reaction kettle of 50 milliliters, 160
oc reaction after 15 hours is filtered reaction product, with 25
oc washed with de-ionized water is removed impurity.By reaction product 100
oafter C vacuum-drying 4 hours, then be placed in high temperature process furnances 1000
oc heating 2 hours, heat-up rate 5
oc per minute, 30 milliliters of per minutes of argon flow amount, naturally cool to after room temperature, by 15 mol/L phosphoric acid 70
oc soaks 6 hours except detin and iron, obtain the graphitized carbon ball that phosphorus doping has hollow structure, its external diameter 117 nanometers, internal diameter 65 nanometers, the ratio of external diameter/internal diameter is 1.8, carbon shell pore size (0.7 nanometer, 1.1 nanometers), mesoporous size 4.7 nanometers of carbon core, approximately 594 square metres every gram of specific surface area, greying ratio is 98.3%, and phosphorus content is 9.2%.
embodiment 6:first by 6.0 grams of glucose, 0.12 gram of sodium stannate, 0.36 gram of iron(ic) chloride, mol ratio 75:1:3, is dissolved in the deionized water of 10 milliliters and the mixed solution of 30 milliliters of phosphoric acid (phosphoric acid concentration 52% ~ 54%), moves into the hydrothermal reaction kettle of 50 milliliters, 160 after stirring
oc reaction after 15 hours is filtered reaction product, with 80
oc washed with de-ionized water is removed impurity.By reaction product 100
oafter C vacuum-drying 4 hours, then be placed in high temperature process furnances 1000
oc heating 2 hours, heat-up rate 5
oc per minute, 30 milliliters of per minutes of argon flow amount, air-cooled to room temperature, by 15 mol/L nitric acid 80
oc soaks 2 hours except detin and iron, obtain the graphitized carbon ball that phosphorus doping has hollow structure, its external diameter 200 nanometers, internal diameter 80 nanometers, the ratio of external diameter/internal diameter is 2.5, carbon shell pore size (0.7 nanometer, 1.1 nanometers), mesoporous size 4.7 nanometers of carbon core, approximately 440 square metres every gram of specific surface area, greying ratio is 99.8%, and phosphorus content is 4.3%.
embodiment 7:first by 8.0 grams of glucose, 0.12 gram of sodium stannate, 0.6 gram of iron(ic) chloride, mol ratio 100:1:5, is dissolved in the deionized water of 20 milliliters and the mixed solution of 20 milliliters of phosphoric acid (phosphoric acid concentration 52% ~ 54%), moves into the hydrothermal reaction kettle of 50 milliliters, 160 after stirring
oc reaction after 15 hours is filtered reaction product, with 100
oc washed with de-ionized water is removed impurity.By reaction product 100
oafter C vacuum-drying 4 hours, then be placed in high temperature process furnances 900
oc heating 2 hours, heat-up rate 5
oc per minute, 30 milliliters of per minutes of nitrogen flow, naturally cool to after room temperature, by 1 mol/L perchloric acid 80
oc soaks 2 hours except detin and iron, obtain the graphitized carbon ball that phosphorus doping has hollow structure, its external diameter 133 nanometers, internal diameter 45 nanometers, the ratio of external diameter/internal diameter is 3.0, carbon shell pore size (0.7 nanometer, 1.1 nanometers), mesoporous size 4.7 nanometers of carbon core, approximately 498 square metres every gram of specific surface area, greying ratio is 97.7%, and phosphorus content is 5.1%.
embodiment 8:first by 10.0 grams of glucose, 0.1 gram of sodium stannate, 0.5 gram of iron(ic) chloride, mol ratio 150:1:5, is dissolved in the deionized water of 10 milliliters and the mixed solution of 30 milliliters of phosphoric acid (phosphoric acid concentration 52% ~ 54%), moves into the hydrothermal reaction kettle of 50 milliliters, 160 after stirring
oc reaction after 15 hours is filtered reaction product, with 100
oc washed with de-ionized water is removed impurity.By reaction product 100
oafter C vacuum-drying 4 hours, then be placed in high temperature process furnances 800
oc heating 2 hours, heat-up rate 5
oc per minute, 30 milliliters of per minutes of nitrogen flow, naturally cool to after room temperature, by 5 mol/L hyperbromic acids 80
oc soaks 2 hours except detin and iron, obtain the graphitized carbon ball that phosphorus doping has hollow structure, its external diameter 200 nanometers, internal diameter 67 nanometers, the ratio of external diameter/internal diameter is 3.0, pore size (0.7 nanometer, 1.1 nanometers) mesoporous size 4.7 nanometers, approximately 453 square metres every gram of specific surface area, greying ratio is 98.3%, phosphorus content is 3.2%.
embodiment 9:first by 4.0 grams of glucose, 0.19 gram of stannous sulfate, 0.29 gram of Tripotassium iron hexacyanide, mol ratio 25:1:1, is dissolved in the deionized water of 10 milliliters and the mixed solution of 30 milliliters of phosphoric acid (phosphoric acid concentration 52% ~ 54%), moves into the hydrothermal reaction kettle of 50 milliliters, 180 after stirring
oc reaction after 8 hours is filtered reaction product, with 100
oc washed with de-ionized water is removed impurity.By reaction product 100
oafter C vacuum-drying 2 hours, then be placed in high temperature process furnances 1000
oc heating 2 hours, heat-up rate 5
oc per minute, 10 milliliters of per minutes of nitrogen flow, naturally cool to after room temperature, by 1 mol/L hydrochloric acid 80
oc soaks 2 hours except detin and iron, obtain the graphitized carbon ball that phosphorus doping has hollow structure, its external diameter 224 nanometers, internal diameter 140 nanometers, the ratio of external diameter/internal diameter is 1.6, carbon shell pore size (0.7 nanometer, 1.1 nanometers), mesoporous size 4.7 nanometers of carbon core, approximately 420 square metres every gram of specific surface area, greying ratio is 99.8%, and phosphorus content is 2.1%.
embodiment 10:first by 8.0 grams of sucrose, 0.17 gram of zinc acetate, 0.23 gram of Cobaltous diacetate, mol ratio 25:1:1, is dissolved in the deionized water of 40 milliliters, moves into the hydrothermal reaction kettle of 50 milliliters, 180 after stirring
oc reaction after 6 hours is filtered reaction product, with 100
oc washed with de-ionized water is removed impurity.By reaction product 100
oafter C vacuum-drying 2 hours, then be placed in high temperature process furnances 1000
oc heating 1 hour, heat-up rate 10
oc per minute, 20 milliliters of per minutes of helium gas flow, naturally cool to after room temperature, by 5 mol/L phosphoric acid 80
oc soaks 2 hours except dezincify and cobalt, obtain the graphitized carbon ball that phosphorus doping has hollow structure, its external diameter 130 nanometers, internal diameter 85 nanometers, the ratio of external diameter/internal diameter is 1.5, carbon shell pore size (0.9 nanometer, 1.3 nanometers), mesoporous size 5.0 nanometers of carbon core, approximately 451 square metres every gram of specific surface area, greying ratio is 99.9%, and phosphorus content is 2.7%.
embodiment 11:first by 8.0 grams of sucrose, 0.13 gram of zinc chloride, 1.16 grams of nickelous acetates, mol ratio 25:1:5, is dissolved in 40 milliliters containing the aqueous solution of 15 grams of disodium-hydrogens, moves into the hydrothermal reaction kettle of 50 milliliters, 180 after stirring
oc reaction after 4 hours is filtered reaction product, with 50
oc washed with de-ionized water is removed impurity.By reaction product 150
ounder C argon shield, be dried 1 hour, then be placed in high temperature process furnances 1200
oc heating 0.5 hour, heat-up rate 10
oc per minute, 40 milliliters of per minutes of nitrogen flow, naturally cool to after room temperature, by 2 mol/L phosphoric acid 80
oc soaks 1 hour except dezincify and nickel, obtain the graphitized carbon ball that phosphorus doping has hollow structure, its external diameter 100 nanometers, internal diameter 75 nanometers, the ratio of external diameter/internal diameter is 1.3, carbon shell pore size (0.9 nanometer, 1.3 nanometers), mesoporous size 5.0 nanometers of carbon core, approximately 518 square metres every gram of specific surface area, greying ratio is 99.8%, and phosphorus content is 4.3%.
embodiment 12:first by 13.4 grams of polyoxyethylene glycol, 0.1 gram of tin tetrachloride, 0.2 gram of iron(ic) chloride, mol ratio 50:1:2, is dissolved in the deionized water of 20 milliliters and the mixed solution of 20 milliliters of polyphosphoric acid, moves into the hydrothermal reaction kettle of 50 milliliters, 180 after stirring
oc reaction after 4 hours is carried out reaction product centrifugal, with 100
oc washed with de-ionized water is removed impurity.By under reaction product nitrogen protection 150
odry 1 hour of C, then be placed in high temperature process furnances 1000
oc heating 1 hour, heat-up rate 10
oc per minute, 10 milliliters of per minutes of argon flow amount, naturally cool to after room temperature, by 1 mol/L hydrochloric acid 80
oc soaks 1 hour except detin and iron, obtain the graphitized carbon ball that phosphorus doping has hollow structure, its external diameter 141 nanometers, internal diameter 105 nanometers, the ratio of external diameter/internal diameter is 1.4, carbon shell pore size (0.7 nanometer, 1.1 nanometers), mesoporous size 4.7 nanometers of carbon core, approximately 497 square metres every gram of specific surface area, greying ratio is 99.8%, and phosphorus content is 4.1%.
embodiment 13:first by 6.0 grams of polyvinyl alcohol, 0.29 gram of zinc sulfate, 2.11 grams of cobalt chloride, mol ratio 75:1:5, is dissolved in the deionized water of 10 milliliters and the mixed solution of 30 milliliters of phosphoric acid (phosphoric acid concentration 52% ~ 54%), moves into the hydrothermal reaction kettle of 50 milliliters, 180 after stirring
oc reaction after 4 hours is filtered reaction product, with 25
oc washed with de-ionized water is removed impurity.By reaction product 120
oafter C vacuum-drying 4 hours, then be placed in high temperature process furnances 700
oc heating 2 hours, heat-up rate 5
oc per minute, 20 milliliters of per minutes of nitrogen flow, naturally cool to after room temperature, by 5 mol/L hydrochloric acid 50
oc soaks 2 hours except dezincify and cobalt, obtain the graphitized carbon ball that phosphorus doping has hollow structure, its external diameter 135 nanometers, internal diameter 110 nanometers, the ratio of external diameter/internal diameter is 1.2, carbon shell pore size (0.9 nanometer, 1.3 nanometers), mesoporous size 5.0 nanometers of carbon core, approximately 543 square metres every gram of specific surface area, greying ratio is 99.8%, and phosphorus content is 5.8%.
embodiment 14:first by 10.4 grams of polyvinyl alcohol, 1.12 grams of sodium stannates, 1.14 grams of iron(ic) chloride, mol ratio 25:1:1, is dissolved in the deionized water of 20 milliliters and the mixed solution of 20 milliliters of phosphoric acid (phosphoric acid concentration 52% ~ 54%), moves into the hydrothermal reaction kettle of 50 milliliters, 230 after stirring
oc reaction after 2 hours is filtered reaction product, with 80
oc washed with de-ionized water is removed impurity.By reaction product 120
oafter C vacuum-drying 2 hours, then be placed in high temperature process furnances 1000
oc heating 1 hour, heat-up rate 10
oc per minute, 50 milliliters of per minutes of nitrogen flow, naturally cool to after room temperature, by 12 mol/L phosphoric acid 80
oc soaks 1 hour except detin and iron, obtain the graphitized carbon ball that phosphorus doping has hollow structure, its external diameter 107 nanometers, internal diameter 85 nanometers, the ratio of external diameter/internal diameter is 1.3, carbon shell pore size (0.7 nanometer, 1.1 nanometers), mesoporous size 4.7 nanometers of carbon core, approximately 631 square metres every gram of specific surface area, greying ratio is 98.9%, and phosphorus content is 15.3%.
embodiment 15:first by 11.3 grams of HMPA, 0.1 gram of sodium stannate, 2.0 grams of cobalt chloride, mol ratio 75:1:10, be dissolved in the deionized water of 30 milliliters and the mixed solution of 10 milliliters of phosphoric acid (phosphoric acid concentration 52% ~ 54%), after stirring, move into the hydrothermal reaction kettle of 50 milliliters, 190
oc reaction after 2 hours is filtered reaction product, with 80
oc washed with de-ionized water is removed impurity.By reaction product 120
oafter C vacuum-drying 2 hours, then be placed in high temperature process furnances 1200
oc heating 1 hour, heat-up rate 10
oc per minute, 15 milliliters of per minutes of argon flow amount, naturally cool to after room temperature, by 3 mol/L hydrochloric acid 50
oc soaks 1 hour except detin and cobalt, obtain the graphitized carbon ball that phosphorus doping has hollow structure, its external diameter 133 nanometers, internal diameter 90 nanometers, the ratio of external diameter/internal diameter is 1.5, carbon shell pore size (0.7 nanometer, 1.1 nanometers), mesoporous size 4.7 nanometers of carbon core, approximately 510 square metres every gram of specific surface area, greying ratio is 99.9%, and phosphorus content is 5.3%.
embodiment 16:first by 7.6 grams of glucose, 0.2 gram of sodium stannate, 0.4 gram of cobalt chloride, mol ratio 25:1:1, is dissolved in the deionized water of 30 milliliters and the mixed solution of 10 milliliters of phosphoric acid (phosphoric acid concentration 52% ~ 54%), moves into the hydrothermal reaction kettle of 50 milliliters, 180 after stirring
oc reaction after 4 hours is filtered reaction product, with 25
oc washed with de-ionized water is removed impurity.By reaction product 100
oafter C vacuum-drying 4 hours, then be placed in high temperature process furnances 900
oc heating 2 hours, heat-up rate 5
oc per minute, 10 milliliters of per minutes of nitrogen flow, naturally cool to after room temperature, by the acid of 5 mol/L phosphoric acid/mixed in hydrochloric acid, volume ratio 1:3,50
oc soaks 1 hour except detin and cobalt, obtain the graphitized carbon ball that phosphorus doping has hollow structure, its external diameter 143 nanometers, internal diameter 114 nanometers, the ratio of external diameter/internal diameter is 1.3, carbon shell pore size (0.7 nanometer, 1.1 nanometers), mesoporous size 4.7 nanometers of carbon core, approximately 489 square metres every gram of specific surface area, greying ratio is 98.3%, and phosphorus content is 4.9%.
embodiment 17:first by 7.6 grams of glucose, 0.2 gram of sodium stannate, 2.0 grams of cobalt chloride, mol ratio 25:1:5, is dissolved in the deionized water of 30 milliliters and the mixed solution of 10 milliliters of phosphoric acid (phosphoric acid concentration 52% ~ 54%), moves into the hydrothermal reaction kettle of 50 milliliters, 180 after stirring
oc reaction after 5 hours is filtered reaction product, with 25
oc washed with de-ionized water is removed impurity.By reaction product 100
oafter C vacuum-drying 4 hours, then be placed in high temperature process furnances 1300
oc heating 0.5 hour, heat-up rate 5
oc per minute, 15 milliliters of per minutes of nitrogen flow, circulating water is to room temperature, by 2 mol/L bromic acids 50
oc soaks 2 hours except detin and cobalt, obtain the graphitized carbon ball that phosphorus doping has hollow structure, its external diameter 148 nanometers, internal diameter 123 nanometers, the ratio of external diameter/internal diameter is 1.2, carbon shell pore size (0.7 nanometer, 1.1 nanometers), mesoporous size 4.7 nanometers of carbon core, approximately 465 square metres every gram of specific surface area, greying ratio is 99.8%, and phosphorus content is 3.5%.
embodiment 18:first by 8.0 grams of polyoxyethylene glycol, 0.12 gram of sodium stannate, 0.13 gram of iron(ic) chloride, mol ratio 25:1:1, is dissolved in 40 milliliters containing the aqueous solution of 10 grams of SODIUM PHOSPHATE, MONOBASIC, moves into the hydrothermal reaction kettle of 50 milliliters, 160 after stirring
oc reaction after 12 hours is filtered reaction product, with 25
oc washed with de-ionized water is removed impurity.By reaction product 100
oafter C vacuum-drying 4 hours, then be placed in high temperature process furnances 700
oc heating 3 hours, heat-up rate 5
oc per minute, 30 milliliters of per minutes of nitrogen flow, naturally cool to after room temperature, by 4 mol/L hydrochloric acid 50
oc soaks 2 hours except detin and iron, obtain the graphitized carbon ball that phosphorus doping has hollow structure, its external diameter 330 nanometers, internal diameter 103 nanometers, the ratio of external diameter/internal diameter is 3.2, carbon shell pore size (0.7 nanometer, 1.1 nanometers), mesoporous size 4.7 nanometers of carbon core, approximately 375 square metres every gram of specific surface area, greying ratio is 98.3%, and phosphorus content is 1.3%.
embodiment 19:first by 8.0 grams of glucose, 0.33 gram of zinc acetate, 0.48 gram of iron(ic) chloride, mol ratio 25:1:1, is dissolved in the deionized water of 30 milliliters and the mixed solution of 10 milliliters of phosphoric acid (phosphoric acid concentration 52% ~ 54%), moves into the hydrothermal reaction kettle of 50 milliliters, 180 after stirring
oc reaction after 4 hours is filtered reaction product, with 25
oc washed with de-ionized water is removed impurity.By reaction product 100
oafter C vacuum-drying 4 hours, then be placed in high temperature process furnances 700
oc heating 3 hours, heat-up rate 5
oc per minute, 30 milliliters of per minutes of nitrogen flow, naturally cool to after room temperature, by 6 mol/L phosphoric acid 80
oc soaks 12 hours except dezincify and iron, obtain the graphitized carbon ball that phosphorus doping has hollow structure, its external diameter 154 nanometers, internal diameter 107 nanometers, the ratio of external diameter/internal diameter is 1.4, carbon shell pore size (0.9 nanometer, 1.3 nanometers), mesoporous size 5.0 nanometers of carbon core, approximately 476 square metres every gram of specific surface area, greying ratio is 97.8%, and phosphorus content is 4.1%.
embodiment 20:first by 8.0 grams of sucrose, 0.14 gram of potassium stannate, 0.13 gram of iron(ic) chloride, mol ratio 50:1:1, is dissolved in the deionized water of 40 milliliters, moves into the hydrothermal reaction kettle of 50 milliliters, 170 after stirring
oc reaction after 5 hours is filtered reaction product, with 25
oc washed with de-ionized water is removed impurity.By reaction product 100
oafter C vacuum-drying 4 hours, then be placed in high temperature process furnances 800
oc heating 3 hours, heat-up rate 5
oc per minute, 30 milliliters of per minutes of nitrogen flow, naturally cool to after room temperature, by 5 mol/L phosphatase 11s 60
oc soaks 4 hours except detin and iron, obtain the graphitized carbon ball that phosphorus doping has hollow structure, its external diameter 195 nanometers, internal diameter 124 nanometers, the ratio of external diameter/internal diameter is 1.6, carbon shell pore size (0.7 nanometer, 1.1 nanometers), mesoporous size 4.7 nanometers of carbon core, approximately 433 square metres every gram of specific surface area, greying ratio is 98.7%, and phosphorus content is 3.8%.
Discussion above and description are giving an example of the specific embodiment of the invention, but they do not mean that the restriction that is subject to this operation.According to the present invention, many improvement and change apparent to those skilled in the art.Claim comprises all equivalence descriptions, defines scope of the present invention.
Claims (1)
1. phosphorus doping has a controllable synthesis method for hollow structure graphitized carbon ball, it is characterized in that: this controllable synthesis method step is:
(1) hydro-thermal is prepared nucleocapsid structure carbon ball
Carbon source, soluble metallic salt, catalyzer are dissolved in solvent according to mol ratio, are stirred to completely and are transferred to hydrothermal reaction kettle Hydrothermal Synthesis after dissolving, by the sediment undergoes washing obtaining, filtration, dry, obtain primary products;
(2) high temperature reduction of carbon ball
In high temperature reaction stove by the primary products that obtain high temperature reduction under gas shield;
(3) prepare hollow plumbago carbon ball
The product that high temperature reduction is obtained is placed in after acidic solution immersion, cleans, filters, is dried, and obtains the graphitized carbon ball that phosphorus doping has hollow structure;
Carbon source in step (1) is for being wherein any one of glucose, sucrose, starch, polyvinyl alcohol, polyoxyethylene glycol, polystyrene, phenol, Resorcinol, toluene, PAPE, diethylene triamine pentamethylene phosphonic or HMPA;
Solvent in step (1) is wherein any one of deionized water, polyphosphoric acid or the phosphorous aqueous solution;
Soluble metallic salt in step (1) is stanniferous metal-salt or the metal-salt that contains zinc, dissolves in 20 ~ 100
othe pure water of C or acidity or basic solution; Wherein stanniferous metal-salt is wherein any one of sodium stannate, potassium stannate, stannous sulfate, stannous oxalate, tindichloride or tin tetrachloride; Containing the metal-salt of zinc, be wherein any one of zinc acetate, zinc iodide, zinc fluoride, zinc chloride, zinc sulfate, zinc phosphate or zinc nitrate;
The metal-salt that described catalyzer in step (1) is iron content or containing the metal-salt of cobalt or nickeliferous metal-salt, dissolves in 20 ~ 100
othe pure water of C or acidity or basic solution; The metal-salt of described iron content is wherein any one of iron(ic) chloride, ferric sulfate, iron nitrate, the Tripotassium iron hexacyanide, yellow prussiate of potash, yellow prussiate of soda, ferrous sulfate, iron protochloride, ferrous ammonium sulphate, ironic acetate, ferric fluoride, ferric ammonium citrate, ironic citrate or Hexacyanoferrate potassium; The described metal-salt containing cobalt is wherein any one of Cobaltous diacetate, rose vitriol, cobalt chloride, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, ammonium cobaltous sulfate or sodium cobaltinitrite; Nickeliferous metal-salt is wherein any one of nickelous bromide, nickelous acetate, single nickel salt, nickelous chloride, nickel ammonium sulfate, nickelous nitrate, nickel sulfamic acid, nickelous fluoride or nickelous carbonate;
The proportioning of the carbon source in step (1), soluble metallic salt, catalyzer is mol ratio 5 ~ 300:1:0.1 ~ 50; In the situation that carbon source content is certain, by adjusting the ratio of soluble metallic salt, regulate the inner/outer diameter ratio of hollow ball, by regulating the ratio of catalyzer and the degree of graphitization that high temperature reduction temperature is adjusted final product;
Hydrothermal Synthesis temperature in step (1) is 100 ~ 300 ℃, 2 ~ 36 hours Hydrothermal Synthesis time;
In step (1) and step (3), for the reagent cleaning, be acetone or alcohol or 20 ~ 100
othe deionized water of C, purging method is for filtration or centrifugal, 60 ~ 300
ounder C vacuum-drying or protection of inert gas, be dried 1 ~ 24 hour; Wherein rare gas element is a kind of or its mixture in nitrogen, argon gas, helium, and proportioning is any, and wherein the purity of nitrogen, argon gas, helium is more than or equal to 99.99%;
Gas in step (2) is a kind of or its mixture in nitrogen, argon gas, helium, hydrogen, and proportioning is any, and wherein the purity of nitrogen, argon gas, helium, hydrogen is more than or equal to 99.99%, and gas flow is 5 ~ 500 ml/min;
High temperature reaction stove in step (2) can time variable control heats up, and passes into gas shield, adopts air-cooled or recirculated water or shallow-layer refrigerated water cooling; Sample is placed in to the middle section of high temperature reaction stove, High Temperature Furnaces Heating Apparatus is retort furnace, tube furnace or microwave oven, and cavity material is quartz, corundum, pottery, stainless steel or insulating brick;
In step (2), the temperature of high temperature reduction is 500 ~ 3200
oc, the recovery time is 0.1 ~ 36 hour, heat-up rate is per minute 0.1 ~ 50
oc;
Acidic solution is acid iodide, phosphoric acid, strong inorganic acid and mixing aqueous acid thereof in step (3), guarantees that pH is less than under 7 prerequisite to mix with arbitrary proportion; When carbon source and solvent are all not phosphorous, in the reagent of pickling, must have a kind of acid is phosphoric acid or the mixing solutions that contains phosphoric acid, and wherein the ratio of phosphoric acid is any and non-vanishing;
The product first high temperature reduction being obtained before soaking in step (3) and acidic solution are ultrasonic or be uniformly mixed to being uniformly dispersed 20 ~ 200
oin C temperature range, soak 0.1 ~ 48 hour, then mixed solution is diluted to cleaning and filtering, and filtrate recycling recycling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310114192.4A CN103183342B (en) | 2013-04-02 | 2013-04-02 | Controllable synthetic method for phosphorus doped graphitization carbon spheres with hollow structures |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310114192.4A CN103183342B (en) | 2013-04-02 | 2013-04-02 | Controllable synthetic method for phosphorus doped graphitization carbon spheres with hollow structures |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103183342A CN103183342A (en) | 2013-07-03 |
| CN103183342B true CN103183342B (en) | 2014-11-12 |
Family
ID=48674834
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310114192.4A Expired - Fee Related CN103183342B (en) | 2013-04-02 | 2013-04-02 | Controllable synthetic method for phosphorus doped graphitization carbon spheres with hollow structures |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103183342B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104201001B (en) * | 2014-07-14 | 2017-02-15 | 上海应用技术学院 | Rod-shaped nitrogen and phosphorus co-doping mesoporous carbon material and preparation method and application thereof |
| CN105013442B (en) * | 2015-07-08 | 2017-05-10 | 中国石油大学(华东) | Preparation method for ordered modified mesoporous carbon material |
| CN105523541B (en) * | 2016-01-29 | 2017-07-18 | 上海交通大学 | Porous carbon tiny balloon of Heteroatom doping and preparation method thereof |
| CN107178006B (en) * | 2017-06-30 | 2018-11-02 | 上海名冠净化材料股份有限公司 | A kind of preparation method of resistant to dissolution type oil-water separation filter paper |
| CN107352527B (en) * | 2017-07-04 | 2019-12-03 | 陕西理工大学 | A kind of carbon nano-tube material preparation process that phosphorus is nitrogen co-doped |
| CN110817834B (en) * | 2018-08-10 | 2022-03-18 | 南京理工大学 | Phosphorus-doped hollow mesoporous carbon sphere material and preparation method thereof |
| CN109395764B (en) * | 2018-12-18 | 2021-09-21 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of phosphorus-doped carbon nitride, product and application thereof |
| CN111744513B (en) * | 2020-07-07 | 2023-07-18 | 上海大学 | Phosphorus doped carbon-based catalyst and application thereof |
| CN113937313A (en) * | 2021-10-13 | 2022-01-14 | 上海应用技术大学 | Preparation method of iron-sulfur-phosphorus co-doped nano porous graphite catalyst |
| CN115212305A (en) * | 2022-05-31 | 2022-10-21 | 同济大学 | New application of magnetic motor |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101264878A (en) * | 2008-04-29 | 2008-09-17 | 山东大学 | All-purpose technique for preparing nano hollow carbon sphere |
| CN102089241A (en) * | 2008-06-10 | 2011-06-08 | 加拿大国家研究委员会 | Controllable synthesis of porous carbon spheres, and electrochemical applications thereof |
| CN101698479B (en) * | 2009-10-30 | 2011-08-17 | 聊城大学 | Preparation method of carbon ball with big size |
| CN102390828B (en) * | 2011-08-03 | 2013-06-19 | 山东大学 | Method for preparing highly-graphitized hollow carbon nanocapsules by using low-temperature reaction |
| CN102637533B (en) * | 2012-04-27 | 2014-03-26 | 黑龙江大学 | Method for preparing nitrogenous graphitized hollow carbon microspheres |
-
2013
- 2013-04-02 CN CN201310114192.4A patent/CN103183342B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN103183342A (en) | 2013-07-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103183330B (en) | Controllable synthesis method for nitrogen and phosphorus co-doped graphitized carbon ball with hollow structure | |
| CN103183342B (en) | Controllable synthetic method for phosphorus doped graphitization carbon spheres with hollow structures | |
| CN103193223A (en) | Controllable synthetic method of graphitized carbon spheres with hollow structure | |
| CN103183341A (en) | Controllable synthesis method of N-doped graphitized carbon ball with hollow structures | |
| CN102992306B (en) | Graphitized carbon with high specific surface area and hierarchical pores and preparation method thereof | |
| US20190126257A1 (en) | Hollow porous carbon nitride nanospheres composite loaded with agbr nanoparticles, preparation method thereof, and its application in dye degradation | |
| CN104148047B (en) | Macro preparation method for carbon doped zinc oxide-based visible-light catalyst | |
| CN102786097A (en) | Hydrothermal preparation method for carbon cladded nanometer ferriferrous oxide particles | |
| CN102600878B (en) | Method for preparing TiC-TiO2 core-shell type nanometer material | |
| CN113368812B (en) | Co3O4Halloysite composite material, preparation method and application | |
| CN106984301B (en) | Manganese cerium titanium catalyst with ordered mesoporous structure, preparation method and application thereof | |
| CN103041795A (en) | Preparation method of titanium dioxide photocatalyst | |
| CN104130004A (en) | Preparation method of high-strength block-shaped porous alumina nano-ceramic | |
| AU2020102823A4 (en) | Method for preparing carbon nanotube-porous carbon composite materials | |
| CN102303861A (en) | Method for preparing mesoporous carbon material based on natural halloysite as template | |
| CN106315690A (en) | Porous cobalt tetroxide nanosheet and preparation method thereof | |
| CN106215968B (en) | A kind of carbon coating CuO composite material and preparation methods of doping nitrogen | |
| CN100486895C (en) | Preparation method for nanometer magnesium oxide | |
| CN102054575A (en) | Method for preparing magnetic mesoporous carbon by co-pouring | |
| CN105293468A (en) | Method for efficiently preparing sulphur-doped hollow carbon spheres | |
| CN112456556A (en) | Method for preparing tantalum oxide nanospheres | |
| CN105060272B (en) | A kind of using artemia chorion as carbon source low temperature under prepare the method for CNT | |
| CN106390930A (en) | Method for preparing silver-loaded activated carbon through glycine and silver nitrate complexation | |
| CN113979466B (en) | ZnO@SiO 2 Method for preparing nanocapsules | |
| CN105271179A (en) | Method for preparing porous wall carbon nano cages through nitrogen doped template |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180419 Address after: 221116 Research Institute of China University of Mining and Technology,, Jiangsu Co-patentee after: Jiangsu Environmental Protection Technology Co. Ltd. Como Patentee after: China University of Mining & Technology Address before: 221008 Research Institute, China University of Mining and Technology, Xuzhou University, Jiangsu, China, Patentee before: China University of Mining & Technology |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141112 Termination date: 20190402 |