CN103183342A - 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
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- CN103183342A CN103183342A CN2013101141924A CN201310114192A CN103183342A CN 103183342 A CN103183342 A CN 103183342A CN 2013101141924 A CN2013101141924 A CN 2013101141924A CN 201310114192 A CN201310114192 A CN 201310114192A CN 103183342 A CN103183342 A CN 103183342A
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- 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 124
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 59
- 239000011574 phosphorus Substances 0.000 title claims abstract description 59
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000005087 graphitization Methods 0.000 title claims abstract description 13
- 238000010189 synthetic method Methods 0.000 title abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 27
- 230000009467 reduction Effects 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 239000000047 product Substances 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 239000003929 acidic solution Substances 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 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 88
- 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 44
- 239000008367 deionised water Substances 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 37
- 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-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 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
- 239000002253 acid Substances 0.000 claims description 11
- 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
- -1 polyoxyethylene Polymers 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 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
- 238000005554 pickling Methods 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-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
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-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
- 229910017604 nitric acid Inorganic materials 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
- 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
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 239000010431 corundum 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
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-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
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 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
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- 238000011084 recovery Methods 0.000 claims description 2
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- 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
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- 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
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- 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
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- 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
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 230000007812 deficiency 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
- 238000005265 energy consumption Methods 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
- 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
- 238000012856 packing Methods 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
- 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
- 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 present invention relates to a kind of synthetic method 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
The nano hollow carbon ball is a kind of special carbon material, have 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, medicine and release template of control, artificial cell, preparation other materials etc., also as various fields such as dyestuff, rubber strongthener, lightweight structural materials, attracted increasing concern.
Hollow carbon sphere is mainly by the preparation of methods such as organism Pintsch process, chemical vapour deposition, medium reduction, laser distillation, arc-over, template self-assembly at present.These methods will be carried out under hot conditions usually, long reaction time, and energy consumption is big, and not only apparatus expensive, complicated operation, cost are higher, and hollow ball shape irregularity productive rate low-purity is not high, has directly influenced suitability for industrialized production and the application thereof of hollow carbon sphere.Therefore explore the technology of low temperature mass preparation hollow carbon sphere, not only help to inquire into theoretically the formation mechanism of hollow carbon sphere, and supply raw materials for its performance of research, help 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 no 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 sizes and pattern by size and the shape of adjusting template.It is template that aluminium meso-porous silica core-shell structure ball is mixed in the ZL200910055527.3 employing, and furfuryl alcohol is carbon source, has prepared small-size meso-porous hollow carbon sphere with removing template silicon-dioxide after its polymerization, the carbonization.ZL200910198399.8 provides a kind of vacuum nano to build the method for preparing the magnetic kernel medium hole hollow carbon sphere, based on the mesoporous SiO 2 hollow ball, by the air pressure inside and outside the change hollow ball, the source of iron solution of different concns is injected in the hollow core, after the thermal treatment furfuryl alcohol is poured on the hollow ball, with utilizing sodium hydroxide solution to remove silica template after its polymerization, the carbonization, obtain having the meso-porous hollow carbon sphere of magnetic kernel.In the whole process of preparation, at first to synthesize template and then will remove the material that template is synthesized at last and do not contain template.This has just caused three problems, and one is to synthesize and remove template to cause the production preparation 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 the hollow material rate ratio is lower; The 3rd, last in removing the process of template, if the strength of materials deficiency that covers may cause structural collapse to cause the synthetic failure of material.
At these shortcomings of template, people explore no template and synthesize hollow carbon material.
ZL200410024700.0, ZL200610027992.2 and ZL200510110213.0 mix the back with metal carbonyls liquid and adopt chemical Vapor deposition process to prepare the nano cages with hollow structure with low-carbon (LC) class organic liquid.Nanjing University's (application number 201210062927.9) is catalyzer with magnesiumcarbonate, adopts chemical Vapor deposition process to prepare the hollow nano cages that nitrogen mixes.Though chemical Vapor deposition process is operated fairly simple, synthetic material shape irregularity, these materials in use tend to show the unstable of structure and the unhomogeneity of performance.Shandong University's (application number 200810015929.6) with oxygen-bearing organic matter as carbon source, the reactor of packing into after mixing with metallic zinc, 500～600 ° of C reactions 4～8 hours obtain the nano hollow carbon ball after pickling.Because adopt metallic zinc as catalyzer and template, the internal diameter variable range of hollow ball is very little.After Heilongjiang University's (application number 201210128545.1) adopts trimeric cyanamide powder and formaldehyde solution hydro-thermal to synthesize again the method for Pintsch process prepared nitrogenous greying hollow carbon sphere, trimeric cyanamide had wherein not only served as template but also as carbon source.Though this method need not be added template and catalyzer in synthetic process, owing to the limitation of trimeric cyanamide powder itself, limited the internal diameter of this hollow carbon sphere equally.ZL200910111112.3 is dissolved in source of iron in the lower alcohol, and mix with the toluene solution that contains tribromophenol or chlorophenesic acid, add the thermal synthesis of nitrogenous source high-temperature water afterwards and 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 the toluene, adopt chemical Vapor deposition process to make the phosphorus doping globular graphite, though 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 behind the high temperature cabonization.(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): be raw material with glucose and sodium stannate 1-10.), hydro-thermal has been synthesized the hollow carbon sphere of Adjustable 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 provides a kind of technology, 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) hydrothermal preparation nucleocapsid structure carbon ball
Carbon source, soluble metallic salt, catalyzer are dissolved in the solvent according to mol ratio, are stirred to fully that to be transferred to the hydrothermal reaction kettle hydro-thermal after the dissolving synthetic, sediment undergoes washing, filtration, drying with obtaining obtain primary products;
(2) high temperature reduction of carbon ball
In high temperature reaction stove with the primary products high temperature reduction under gas shield that obtains;
(3) preparation hollow plumbago carbon ball
After the product that high temperature reduction is obtained placed acidic solution to soak, cleaning, filtration, drying namely obtained the graphitized carbon ball that phosphorus doping has hollow structure;
Carbon source in the 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 the step (1) is wherein any one of deionized water, phosphoric acid, polyphosphoric acid or the phosphorous aqueous solution;
Soluble metallic salt in the step (1) is the metal-salt of stanniferous or the metal-salt that contains zinc, dissolves in pure water or acidity or the basic solution of 20～100 ° of C; Wherein the metal-salt of stanniferous is wherein any one of sodium stannate, potassium stannate, stannous sulfate, stannous oxalate, tindichloride or tin tetrachloride; The metal-salt that contains zinc is wherein any one of zinc acetate, zinc iodide, zinc fluoride, zinc chloride, zinc sulfate, zinc phosphate or zinc nitrate;
Described catalyzer in the step (1) is the metal-salt of iron content or contains the metal-salt of cobalt or nickeliferous metal-salt, dissolves in pure water or acidity or the basic solution of 20～100 ° of C; 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 that contains cobalt is wherein any one of Cobaltous diacetate, rose vitriol, cobalt chloride, Xiao Suangu, 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 the step (1), soluble metallic salt, catalyzer is mol ratio 5～300:1:0.1～50; Under the certain situation of carbon source content, the inner/outer diameter ratio that can regulate hollow ball by the ratio of adjusting soluble metallic salt is by the ratio of regulating catalyzer and the degree of graphitization that the high temperature reduction temperature is adjusted final product;
Hydro-thermal synthesis temperature in the step (1) is 100～300 ° of C, hydro-thermal generated time 2～36 hours;
The reagent that is used in step (1) and the step (3) cleaning is the deionized water of acetone or alcohol or 20～100 ° of C, and purging method is filtration or centrifugal, and drying is 1～24 hour under 60～300 ° of C vacuum-dryings or protection of inert gas; Wherein rare gas element is a kind of or its mixture in nitrogen, argon gas, the helium, and proportioning is any, and wherein the purity of nitrogen, argon gas, helium is more than or equal to 99.99%;
Gas in the step (2) is a kind of or its mixture in nitrogen, argon gas, helium, the 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;
Step (2) but in the high temperature reaction stove time variable control heat up, can feed gas shield, adopts air-cooled or recirculated water or shallow-layer refrigerated water cool off; Sample is placed the middle section of high temperature reaction stove, and 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;
The temperature of high temperature reduction is 500～3200 ° of C in the step (2), and the recovery time is 0.1～36 hour, and heat-up rate is 0.1～50 ° of C of per minute;
Acidic solution is hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acid iodide, bromic acid, perchloric acid, Periodic acid, hyperbromic acid, permanganic acid, dichromic acid strong inorganic acid and mixes aqueous acid in the step (3), guarantees that the pH value of solution value is less than mixing with arbitrary proportion under 7 the prerequisite; When carbon source and solvent were all not phosphorous, it was phosphoric acid or the mixed solution that contains phosphoric acid that a kind of acid must be arranged in the reagent of pickling, and wherein the ratio of phosphoric acid is any and non-vanishing;
The product that earlier high temperature reduction is obtained before soaking in the step (3) and acidic solution are ultrasonic or mix to being uniformly dispersed, and soak 0.1～48 hour in 20～200 ° of C temperature ranges, then mixed solution are diluted cleaning and filtering, and filtrate recycling recycling.
Beneficial effect, owing to adopted such scheme, the preparation method of this phosphorus doping hollow structure graphitized carbon ball, products obtained therefrom purity height, substantially free from foreign meter, pattern is even, the carbon shell has microvoid structure, carbon ball inside has the mesoporous carbon supporting structure, degree of graphitization is good.By regulating the ratio that carbon source and ratio or the kind of soluble metallic salt are controlled the inner/outer diameter of hollow carbon sphere, and micropore and mesoporous ratio.By ratio and the high temperature reduction temperature control degree of graphitization of adjusting catalyzer.By regulate carbon source kind or hydro-thermal synthetic in the content of concentration control phosphorus of the content of phosphorus or hydrothermal temperature or hydro-thermal time or pickling temperature or pickling time or phosphoric acid solution.Soluble metallic salt and catalyzer as presoma are cheap, and recycling easily can reduce cost environmental protection.Hollow structure graphitized carbon ball has and the diverse characteristic of conventional graphite material, can be used as catalytic material and be used for the efficient catalytic conversion, be used for energy storage and conversion as electrode materials, be used for medicine as pharmaceutical carrier and release control, being used for storage hydrogen as the gas storage medium separates with gas trapping, as filtering adsorbing material be used for separating substances, as template for the preparation of other nano materials, as electrode materials, be used for various fields such as rubber and resin enhancing as conductive agent as the lightweight strongthener.
Advantage: technology is simple, with low cost, the product purity height, the phosphorus doping hollow structure graphitized carbon ball that makes have pattern evenly, the carbon shell has that microvoid structure, carbon ball inside have the mesoporous carbon supporting structure, degree of graphitization is good, can be used for efficient catalytic conversion, energy storage and conversion, medicine is released various fields such as control, material fractionation by adsorption, atmosphere storage.
Embodiment
Below by embodiment in detail the present invention is described in detail.
Embodiment 1: at first with 4.0 gram glucose, 0.21 gram sodium stannate, 0.22 gram iron(ic) chloride, mol ratio 25:1:1, be dissolved in 40 ml deionized water, move into 50 milliliters hydrothermal reaction kettle after stirring, 160 ° of C reactions after 15 hours are filtered reaction product, remove impurity with 25 ° of C washed with de-ionized water.With 70 ° of C vacuum-dryings of reaction product after 12 hours, place 1000 ° of C heating of high temperature process furnances 2 hours again, 5 ° of C per minutes of heat-up rate, 30 milliliters of per minutes of nitrogen flow, after naturally cooling to room temperature, soak 6 hours except detin and iron by 0 ° of C of 14mol/L phosphatase 79, 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), carbon is examined mesoporous size 4.7 nanometers, the about 420 square metres of every grams of specific surface area, the greying ratio is 98.9%, phosphorus content is 1.7%.
The soluble metallic salt that adds is the metal-salt of stanniferous or the metal-salt that contains zinc, and the fusing point of this two classes salt is very low, flows out from the carbon shell easily during heat, forms to have mesoporous hollow carbon.
Adding catalyzer is in order to reduce graphitization temperature, to reach the purpose that cuts down the consumption of energy.
Under the certain situation of carbon source content, the inner/outer diameter ratio that can regulate hollow ball by the ratio of adjusting soluble metallic salt is by the ratio of regulating catalyzer and the degree of graphitization that the high temperature reduction temperature is adjusted final product.
By regulate carbon source kind or hydro-thermal synthetic in the content of concentration control phosphorus of the content of phosphorus or hydrothermal temperature or hydro-thermal time or pickling temperature or pickling time or phosphoric acid solution.
Control heat-up rate well, the too fast structure that can not obtain wishing of heat-up rate, heat-up rate is crossed slowly can cause energy dissipation.
The acidic solution that adopts can not produce destruction to the structure of graphitized carbon material, therefore do not have concentration limit, but had better not use strong solution, but concentration can not be too low, otherwise can cause the removal decrease in efficiency.
Embodiment 2: at first with 4.0 gram glucose, 0.21 gram sodium stannate, 0.22 gram iron(ic) chloride, mol ratio 25:1:1, be dissolved in 20 milliliters deionized water and the mixed solution of 20 milliliters of phosphoric acid (phosphoric acid concentration 52%～54%), move into 50 milliliters hydrothermal reaction kettle after stirring, 160 ° of C reactions after 3 hours are filtered reaction product, remove impurity with 25 ° of C washed with de-ionized water.With 100 ° of C vacuum-dryings of reaction product after 4 hours, place 1000 ° of C heating of high temperature process furnances 2 hours again, 5 ° of C per minutes of heat-up rate, 30 milliliters of per minutes of nitrogen flow, after naturally cooling to room temperature, soak 6 hours except detin and iron by 0 ° of C of 5mol/L phosphatase 79, 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), carbon is examined mesoporous size 4.7 nanometers, the about 521 square metres of every grams of specific surface area, the greying ratio is 97.8%, phosphorus content is 7.2%.
Embodiment 3: at first with 4.0 gram glucose, 0.21 gram sodium stannate, 0.22 gram iron(ic) chloride, mol ratio 25:1:1, be dissolved in 10 milliliters deionized water and the mixed solution of 30 milliliters of phosphoric acid (phosphoric acid concentration 52%～54%), move into 50 milliliters hydrothermal reaction kettle after stirring, 160 ° of C reactions after 9 hours are filtered reaction product, remove impurity with 50 ° of C washed with de-ionized water.With 100 ° of C vacuum-dryings of reaction product after 4 hours, place 1000 ° of C heating of high temperature process furnances 2 hours again, 5 ° of C per minutes of heat-up rate, 30 milliliters of per minutes of nitrogen flow, after naturally cooling to room temperature, soak 6 hours except detin and iron by 0 ° of C of 2mol/L phosphatase 79, 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), carbon is examined mesoporous size 4.7 nanometers, the about 530 square metres of every grams of specific surface area, the greying ratio is 98.7%, phosphorus content is 6.9%.
Embodiment 4: at first with 4.0 gram glucose, 1.07 gram sodium stannates, 1.08 gram iron(ic) chloride, mol ratio 5:1:1, be dissolved in 40 milliliters of aqueous solution that contain 10 gram sodium phosphates, move into 50 milliliters hydrothermal reaction kettle after stirring, 160 ° of C reactions after 15 hours are filtered reaction product, remove impurity with 25 ° of C washed with de-ionized water.With 150 ° of C vacuum-dryings of reaction product after 2 hours, place 700 ° of C heating of high temperature process furnances 2 hours again, 5 ° of C per minutes of heat-up rate, 30 milliliters of per minutes of nitrogen flow, after naturally cooling to room temperature, soak 12 hours except detin and iron by 75 ° of C of 1mol/L sulfuric acid, 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), carbon is examined mesoporous size 4.7 nanometers, the about 572 square metres of every grams of specific surface area, the greying ratio is 99.8%, phosphorus content is 7.3%.
Embodiment 5: at first with 8.0 gram glucose, 0.24 gram sodium stannate, 0.24 gram iron(ic) chloride mol ratio 50:1:1, be dissolved in 10 milliliters deionized water and the mixed solution of 30 milliliters of phosphoric acid (phosphoric acid concentration 52%～54%), move into 50 milliliters hydrothermal reaction kettle after stirring, 160 ° of C reactions after 15 hours are filtered reaction product, remove impurity with 25 ° of C washed with de-ionized water.With 100 ° of C vacuum-dryings of reaction product after 4 hours, place 1000 ° of C heating of high temperature process furnances 2 hours again, 5 ° of C per minutes of heat-up rate, 30 milliliters of per minutes of argon flow amount, after naturally cooling to room temperature, soak 6 hours except detin and iron by 70 ° of C of 15mol/L phosphoric acid, 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), carbon is examined mesoporous size 4.7 nanometers, the about 594 square metres of every grams of specific surface area, the greying ratio is 98.3%, phosphorus content is 9.2%.
Embodiment 6: at first with 6.0 gram glucose, 0.12 gram sodium stannate, 0.36 gram iron(ic) chloride, mol ratio 75:1:3, be dissolved in 10 milliliters deionized water and the mixed solution of 30 milliliters of phosphoric acid (phosphoric acid concentration 52%～54%), move into 50 milliliters hydrothermal reaction kettle after stirring, 160 ° of C reactions after 15 hours are filtered reaction product, remove impurity with 80 ° of C washed with de-ionized water.With 100 ° of C vacuum-dryings of reaction product after 4 hours, place 1000 ° of C heating of high temperature process furnances 2 hours again, 5 ° of C per minutes of heat-up rate, 30 milliliters of per minutes of argon flow amount, air-cooled to room temperature, soak 2 hours except detin and iron by 80 ° of C of 15mol/L nitric acid, 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), carbon is examined mesoporous size 4.7 nanometers, the about 440 square metres of every grams of specific surface area, the greying ratio is 99.8%, phosphorus content is 4.3%.
Embodiment 7: at first with 8.0 gram glucose, 0.12 gram sodium stannate, 0.6 gram iron(ic) chloride, mol ratio 100:1:5, be dissolved in 20 milliliters deionized water and the mixed solution of 20 milliliters of phosphoric acid (phosphoric acid concentration 52%～54%), move into 50 milliliters hydrothermal reaction kettle after stirring, 160 ° of C reactions after 15 hours are filtered reaction product, remove impurity with 100 ° of C washed with de-ionized water.With 100 ° of C vacuum-dryings of reaction product after 4 hours, place 900 ° of C heating of high temperature process furnances 2 hours again, 5 ° of C per minutes of heat-up rate, 30 milliliters of per minutes of nitrogen flow, after naturally cooling to room temperature, soak 2 hours except detin and iron by 80 ° of C of 1mol/L perchloric acid, 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), carbon is examined mesoporous size 4.7 nanometers, the about 498 square metres of every grams of specific surface area, the greying ratio is 97.7%, phosphorus content is 5.1%.
Embodiment 8: at first with 10.0 gram glucose, 0.1 gram sodium stannate, 0.5 gram iron(ic) chloride, mol ratio 150:1:5, be dissolved in 10 milliliters deionized water and the mixed solution of 30 milliliters of phosphoric acid (phosphoric acid concentration 52%～54%), move into 50 milliliters hydrothermal reaction kettle after stirring, 160 ° of C reactions after 15 hours are filtered reaction product, remove impurity with 100 ° of C washed with de-ionized water.With 100 ° of C vacuum-dryings of reaction product after 4 hours, place 800 ° of C heating of high temperature process furnances 2 hours again, 5 ° of C per minutes of heat-up rate, 30 milliliters of per minutes of nitrogen flow, after naturally cooling to room temperature, soak 2 hours except detin and iron by 80 ° of C of 5mol/L hyperbromic acid, 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, mesoporous size 4.7 nanometers of pore size (0.7 nanometer, 1.1 nanometers), the about 453 square metres of every grams of specific surface area, the greying ratio is 98.3%, and phosphorus content is 3.2%.
Embodiment 9: at first with 4.0 gram glucose, 0.19 gram stannous sulfate, the 0.29 gram Tripotassium iron hexacyanide, mol ratio 25:1:1, be dissolved in 10 milliliters deionized water and the mixed solution of 30 milliliters of phosphoric acid (phosphoric acid concentration 52%～54%), move into 50 milliliters hydrothermal reaction kettle after stirring, 180 ° of C reactions after 8 hours are filtered reaction product, remove impurity with 100 ° of C washed with de-ionized water.With 100 ° of C vacuum-dryings of reaction product after 2 hours, place 1000 ° of C heating of high temperature process furnances 2 hours again, 5 ° of C per minutes of heat-up rate, 10 milliliters of per minutes of nitrogen flow, after naturally cooling to room temperature, soak 2 hours except detin and iron by 80 ° of C of 1mol/L hydrochloric acid, 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), carbon is examined mesoporous size 4.7 nanometers, the about 420 square metres of every grams of specific surface area, the greying ratio is 99.8%, phosphorus content is 2.1%.
Embodiment 10: at first with 8.0 gram sucrose, 0.17 gram zinc acetate, 0.23 gram Cobaltous diacetate, mol ratio 25:1:1, be dissolved in 40 milliliters deionized water, move into 50 milliliters hydrothermal reaction kettle after stirring, 180 ° of C reactions after 6 hours are filtered reaction product, remove impurity with 100 ° of C washed with de-ionized water.With 100 ° of C vacuum-dryings of reaction product after 2 hours, place 1000 ° of C heating of high temperature process furnances 1 hour again, 10 ° of C per minutes of heat-up rate, 20 milliliters of per minutes of helium gas flow, after naturally cooling to room temperature, soak 2 hours except dezincify and cobalt by 80 ° of C of 5mol/L phosphoric acid, 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), carbon is examined mesoporous size 5.0 nanometers, the about 451 square metres of every grams of specific surface area, the greying ratio is 99.9%, phosphorus content is 2.7%.
Embodiment 11: at first with 8.0 gram sucrose, 0.13 gram zinc chloride, 1.16 gram nickelous acetates, mol ratio 25:1:5, be dissolved in 40 milliliters of aqueous solution that contain 15 gram disodium-hydrogens, move into 50 milliliters hydrothermal reaction kettle after stirring, 180 ° of C reactions after 4 hours are filtered reaction product, remove impurity with 50 ° of C washed with de-ionized water.With under 150 ° of C argon shields of reaction product dry 1 hour; place 1200 ° of C heating of high temperature process furnances 0.5 hour again; 10 ° of C per minutes of heat-up rate; 40 milliliters of per minutes of nitrogen flow; after naturally cooling to room temperature; soak 1 hour except dezincify and nickel by 80 ° of C of 2mol/L phosphoric acid, 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); carbon is examined mesoporous size 5.0 nanometers; the about 518 square metres of every grams of specific surface area, the greying ratio is 99.8%, phosphorus content is 4.3%.
Embodiment 12: at first with 13.4 gram polyoxyethylene glycol, 0.1 gram tin tetrachloride, 0.2 gram iron(ic) chloride, mol ratio 50:1:2, be dissolved in 20 milliliters deionized water and the mixed solution of 20 milliliters of polyphosphoric acid, move into 50 milliliters hydrothermal reaction kettle after stirring, 180 ° of C reaction after 4 hours is carried out reaction product centrifugal, removes impurity with 100 ° of C washed with de-ionized water.With dry 1 hour of the following 150 ° of C of reaction product nitrogen protection; place 1000 ° of C heating of high temperature process furnances 1 hour again; 10 ° of C per minutes of heat-up rate; 10 milliliters of per minutes of argon flow amount; after naturally cooling to room temperature; soak 1 hour except detin and iron by 80 ° of C of 1mol/L hydrochloric acid, 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); carbon is examined mesoporous size 4.7 nanometers; the about 497 square metres of every grams of specific surface area, the greying ratio is 99.8%, phosphorus content is 4.1%.
Embodiment 13: at first with 6.0 gram polyvinyl alcohol, 0.29 gram zinc sulfate, 2.11 gram cobalt chloride, mol ratio 75:1:5, be dissolved in 10 milliliters deionized water and the mixed solution of 30 milliliters of phosphoric acid (phosphoric acid concentration 52%～54%), move into 50 milliliters hydrothermal reaction kettle after stirring, 180 ° of C reactions after 4 hours are filtered reaction product, remove impurity with 25 ° of C washed with de-ionized water.With 120 ° of C vacuum-dryings of reaction product after 4 hours, place 700 ° of C heating of high temperature process furnances 2 hours again, 5 ° of C per minutes of heat-up rate, 20 milliliters of per minutes of nitrogen flow, after naturally cooling to room temperature, soak 2 hours except dezincify and cobalt by 50 ° of C of 5mol/L hydrochloric acid, 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), carbon is examined mesoporous size 5.0 nanometers, the about 543 square metres of every grams of specific surface area, the greying ratio is 99.8%, phosphorus content is 5.8%.
Embodiment 14: at first with 10.4 gram polyvinyl alcohol, 1.12 gram sodium stannates, 1.14 gram iron(ic) chloride, mol ratio 25:1:1, be dissolved in 20 milliliters deionized water and the mixed solution of 20 milliliters of phosphoric acid (phosphoric acid concentration 52%～54%), move into 50 milliliters hydrothermal reaction kettle after stirring, 230 ° of C reactions after 2 hours are filtered reaction product, remove impurity with 80 ° of C washed with de-ionized water.With 120 ° of C vacuum-dryings of reaction product after 2 hours, place 1000 ° of C heating of high temperature process furnances 1 hour again, 10 ° of C per minutes of heat-up rate, 50 milliliters of per minutes of nitrogen flow, after naturally cooling to room temperature, soak 1 hour except detin and iron by 80 ° of C of 12mol/L phosphoric acid, 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), carbon is examined mesoporous size 4.7 nanometers, the about 631 square metres of every grams of specific surface area, the greying ratio is 98.9%, phosphorus content is 15.3%.
Embodiment 15: at first with 11.3 gram HMPA, 0.1 gram sodium stannate, 2.0 gram cobalt chloride, mol ratio 75:1:10, be dissolved in 30 milliliters deionized water and the mixed solution of 10 milliliters of phosphoric acid (phosphoric acid concentration 52%～54%), move into 50 milliliters hydrothermal reaction kettle after stirring, 190 ° of C reactions after 2 hours are filtered reaction product, remove impurity with 80 ° of C washed with de-ionized water.With 120 ° of C vacuum-dryings of reaction product after 2 hours, place 1200 ° of C heating of high temperature process furnances 1 hour again, 10 ° of C per minutes of heat-up rate, 15 milliliters of per minutes of argon flow amount, after naturally cooling to room temperature, soak 1 hour except detin and cobalt by 50 ° of C of 3mol/L hydrochloric acid, 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), carbon is examined mesoporous size 4.7 nanometers, the about 510 square metres of every grams of specific surface area, the greying ratio is 99.9%, phosphorus content is 5.3%.
Embodiment 16: at first with 7.6 gram glucose, 0.2 gram sodium stannate, 0.4 gram cobalt chloride, mol ratio 25:1:1, be dissolved in 30 milliliters deionized water and the mixed solution of 10 milliliters of phosphoric acid (phosphoric acid concentration 52%～54%), move into 50 milliliters hydrothermal reaction kettle after stirring, 180 ° of C reactions after 4 hours are filtered reaction product, remove impurity with 25 ° of C washed with de-ionized water.With 100 ° of C vacuum-dryings of reaction product after 4 hours, place 900 ° of C heating of high temperature process furnances 2 hours again, 5 ° of C per minutes of heat-up rate, 10 milliliters of per minutes of nitrogen flow, naturally cool to room temperature after, by 5mol/L phosphoric acid/mixed in hydrochloric acid acid, volume ratio 1:3,50 ° of C soak 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), carbon is examined mesoporous size 4.7 nanometers, the about 489 square metres of every grams of specific surface area, the greying ratio is 98.3%, phosphorus content is 4.9%.
Embodiment 17: at first with 7.6 gram glucose, 0.2 gram sodium stannate, 2.0 gram cobalt chloride, mol ratio 25:1:5, be dissolved in 30 milliliters deionized water and the mixed solution of 10 milliliters of phosphoric acid (phosphoric acid concentration 52%～54%), move into 50 milliliters hydrothermal reaction kettle after stirring, 180 ° of C reactions after 5 hours are filtered reaction product, remove impurity with 25 ° of C washed with de-ionized water.With 100 ° of C vacuum-dryings of reaction product after 4 hours, place 1300 ° of C heating of high temperature process furnances 0.5 hour again, 5 ° of C per minutes of heat-up rate, 15 milliliters of per minutes of nitrogen flow, recirculated water cools off to room temperature, soak 2 hours except detin and cobalt by 50 ° of C of 2mol/L bromic acid, 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), carbon is examined mesoporous size 4.7 nanometers, the about 465 square metres of every grams of specific surface area, the greying ratio is 99.8%, phosphorus content is 3.5%.
Embodiment 18: at first with 8.0 gram polyoxyethylene glycol, 0.12 gram sodium stannate, 0.13 gram iron(ic) chloride, mol ratio 25:1:1, be dissolved in 40 milliliters of aqueous solution that contain 10 gram SODIUM PHOSPHATE, MONOBASIC, move into 50 milliliters hydrothermal reaction kettle after stirring, 160 ° of C reactions after 12 hours are filtered reaction product, remove impurity with 25 ° of C washed with de-ionized water.With 100 ° of C vacuum-dryings of reaction product after 4 hours, place 700 ° of C heating of high temperature process furnances 3 hours again, 5 ° of C per minutes of heat-up rate, 30 milliliters of per minutes of nitrogen flow, after naturally cooling to room temperature, soak 2 hours except detin and iron by 50 ° of C of 4mol/L hydrochloric acid, 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), carbon is examined mesoporous size 4.7 nanometers, the about 375 square metres of every grams of specific surface area, the greying ratio is 98.3%, phosphorus content is 1.3%.
Embodiment 19: at first with 8.0 gram glucose, 0.33 gram zinc acetate, 0.48 gram iron(ic) chloride, mol ratio 25:1:1, be dissolved in 30 milliliters deionized water and the mixed solution of 10 milliliters of phosphoric acid (phosphoric acid concentration 52%～54%), move into 50 milliliters hydrothermal reaction kettle after stirring, 180 ° of C reactions after 4 hours are filtered reaction product, remove impurity with 25 ° of C washed with de-ionized water.With 100 ° of C vacuum-dryings of reaction product after 4 hours, place 700 ° of C heating of high temperature process furnances 3 hours again, 5 ° of C per minutes of heat-up rate, 30 milliliters of per minutes of nitrogen flow, after naturally cooling to room temperature, soak 12 hours except dezincify and iron by 80 ° of C of 6mol/L phosphoric acid, 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), carbon is examined mesoporous size 5.0 nanometers, the about 476 square metres of every grams of specific surface area, the greying ratio is 97.8%, phosphorus content is 4.1%.
Embodiment 20: at first with 8.0 gram sucrose, 0.14 gram potassium stannate, 0.13 gram iron(ic) chloride, mol ratio 50:1:1, be dissolved in 40 milliliters deionized water, move into 50 milliliters hydrothermal reaction kettle after stirring, 170 ° of C reactions after 5 hours are filtered reaction product, remove impurity with 25 ° of C washed with de-ionized water.With 100 ° of C vacuum-dryings of reaction product after 4 hours, place 800 ° of C heating of high temperature process furnances 3 hours again, 5 ° of C per minutes of heat-up rate, 30 milliliters of per minutes of nitrogen flow, after naturally cooling to room temperature, soak 4 hours except detin and iron by 60 ° of C of 5mol/L phosphatase 11, 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), carbon is examined mesoporous size 4.7 nanometers, the about 433 square metres of every grams of specific surface area, the greying ratio is 98.7%, phosphorus content is 3.8%.
The discussion of front and description are giving an example of the specific embodiment of the invention, but they do not mean that the restriction that is subjected 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. a phosphorus doping has the controllable synthesis method of hollow structure graphitized carbon ball, it is characterized in that: this controllable synthesis method, and step is:
(1) hydrothermal preparation nucleocapsid structure carbon ball
Carbon source, soluble metallic salt, catalyzer are dissolved in the solvent according to mol ratio, are stirred to fully that to be transferred to the hydrothermal reaction kettle hydro-thermal after the dissolving synthetic, sediment undergoes washing, filtration, drying with obtaining obtain primary products;
(2) high temperature reduction of carbon ball
In high temperature reaction stove with the primary products high temperature reduction under gas shield that obtains;
(3) preparation hollow plumbago carbon ball
After the product that high temperature reduction is obtained placed acidic solution to soak, cleaning, filtration, drying namely obtained the graphitized carbon ball that phosphorus doping has hollow structure;
Carbon source in the 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 the step (1) is wherein any one of deionized water, phosphoric acid, polyphosphoric acid or the phosphorous aqueous solution;
Soluble metallic salt in the step (1) is the metal-salt of stanniferous or the metal-salt that contains zinc, dissolves in pure water or acidity or the basic solution of 20～100 ° of C; Wherein the metal-salt of stanniferous is wherein any one of sodium stannate, potassium stannate, stannous sulfate, stannous oxalate, tindichloride or tin tetrachloride; The metal-salt that contains zinc is wherein any one of zinc acetate, zinc iodide, zinc fluoride, zinc chloride, zinc sulfate, zinc phosphate or zinc nitrate;
Described catalyzer in the step (1) is the metal-salt of iron content or contains the metal-salt of cobalt or nickeliferous metal-salt, dissolves in pure water or acidity or the basic solution of 20～100 ° of C; 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 that contains cobalt is wherein any one of Cobaltous diacetate, rose vitriol, cobalt chloride, Xiao Suangu, 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 the step (1), soluble metallic salt, catalyzer is mol ratio 5～300:1:0.1～50; Under the certain situation of carbon source content, the inner/outer diameter ratio that can regulate hollow ball by the ratio of adjusting soluble metallic salt is by the ratio of regulating catalyzer and the degree of graphitization that the high temperature reduction temperature is adjusted final product;
Hydro-thermal synthesis temperature in the step (1) is 100～300 ℃, hydro-thermal generated time 2～36 hours;
The reagent that is used in step (1) and the step (3) cleaning is the deionized water of acetone or alcohol or 20～100 ° of C, and purging method is filtration or centrifugal, and drying is 1～24 hour under 60～300 ° of C vacuum-dryings or protection of inert gas; Wherein rare gas element is a kind of or its mixture in nitrogen, argon gas, the helium, and proportioning is any, and wherein the purity of nitrogen, argon gas, helium is more than or equal to 99.99%;
Gas in the step (2) is a kind of or its mixture in nitrogen, argon gas, helium, the 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;
Step (2) but in the high temperature reaction stove time variable control heat up, can feed gas shield, adopts air-cooled or recirculated water or shallow-layer refrigerated water cool off; Sample is placed the middle section of high temperature reaction stove, and 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;
The temperature of high temperature reduction is 500～3200 ° of C in the step (2), and the recovery time is 0.1～36 hour, and heat-up rate is 0.1～50 ° of C of per minute;
Acidic solution is hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acid iodide, bromic acid, perchloric acid, Periodic acid, hyperbromic acid, permanganic acid, dichromic acid strong inorganic acid and mixes aqueous acid in the step (3), guarantees that the pH value of solution value is less than mixing with arbitrary proportion under 7 the prerequisite; When carbon source and solvent were all not phosphorous, it was phosphoric acid or the mixing solutions that contains phosphoric acid that a kind of acid must be arranged in the reagent of pickling, and wherein the ratio of phosphoric acid is any and non-vanishing;
The product that earlier high temperature reduction is obtained before soaking in the step (3) and acidic solution are ultrasonic or mix to being uniformly dispersed, and soak 0.1～48 hour in 20～200 ° of C temperature ranges, then mixed solution are diluted cleaning and filtering, and filtrate recycling recycling.
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