JP5779267B2 - Nitrogen-containing carbon material - Google Patents
Nitrogen-containing carbon material Download PDFInfo
- Publication number
- JP5779267B2 JP5779267B2 JP2014076114A JP2014076114A JP5779267B2 JP 5779267 B2 JP5779267 B2 JP 5779267B2 JP 2014076114 A JP2014076114 A JP 2014076114A JP 2014076114 A JP2014076114 A JP 2014076114A JP 5779267 B2 JP5779267 B2 JP 5779267B2
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- JP
- Japan
- Prior art keywords
- nitrogen
- containing carbon
- carbon material
- acid
- results
- 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.)
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- 239000003575 carbonaceous material Substances 0.000 title claims description 113
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims description 108
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 39
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 229910052723 transition metal Inorganic materials 0.000 claims description 19
- 150000003624 transition metals Chemical group 0.000 claims description 18
- 238000002441 X-ray diffraction Methods 0.000 claims description 16
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 238000010586 diagram Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 description 60
- 239000007864 aqueous solution Substances 0.000 description 50
- 239000002253 acid Substances 0.000 description 48
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 40
- 239000002243 precursor Substances 0.000 description 39
- 238000004458 analytical method Methods 0.000 description 33
- 238000000160 carbon, hydrogen and nitrogen elemental analysis Methods 0.000 description 32
- 238000000034 method Methods 0.000 description 32
- 238000002848 electrochemical method Methods 0.000 description 29
- 239000002904 solvent Substances 0.000 description 28
- 239000000203 mixture Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 19
- 229910052751 metal Inorganic materials 0.000 description 19
- 239000002184 metal Substances 0.000 description 19
- 239000002994 raw material Substances 0.000 description 19
- 238000010298 pulverizing process Methods 0.000 description 16
- 238000005259 measurement Methods 0.000 description 15
- 238000000227 grinding Methods 0.000 description 14
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 description 10
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 10
- 239000010453 quartz Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 8
- 239000000446 fuel Substances 0.000 description 8
- -1 transition metal oxalate Chemical class 0.000 description 8
- 229920000877 Melamine resin Polymers 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000010304 firing Methods 0.000 description 7
- 239000011261 inert gas Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000003763 carbonization Methods 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 6
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 230000000379 polymerizing effect Effects 0.000 description 5
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000004640 Melamine resin Substances 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 4
- 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 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 description 4
- UHKHUAHIAZQAED-UHFFFAOYSA-N phthalocyaninatoiron Chemical compound [Fe].N=1C2=NC(C3=CC=CC=C33)=NC3=NC(C3=CC=CC=C33)=NC3=NC(C3=CC=CC=C33)=NC3=NC=1C1=CC=CC=C12 UHKHUAHIAZQAED-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 150000003141 primary amines Chemical class 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 230000010757 Reduction Activity Effects 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- NOWPEMKUZKNSGG-UHFFFAOYSA-N azane;platinum(2+) Chemical compound N.N.N.N.[Pt+2] NOWPEMKUZKNSGG-UHFFFAOYSA-N 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 150000007530 organic bases Chemical class 0.000 description 3
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VEJOYRPGKZZTJW-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;platinum Chemical compound [Pt].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O VEJOYRPGKZZTJW-FDGPNNRMSA-N 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- QGNQBYHJYKOUCL-UHFFFAOYSA-N CC=1C(=C(C(C=1)(C)[Co]C1(C(=C(C(=C1)C)C)C)C)C)C Chemical compound CC=1C(=C(C(C=1)(C)[Co]C1(C(=C(C(=C1)C)C)C)C)C)C QGNQBYHJYKOUCL-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- PMVSDNDAUGGCCE-TYYBGVCCSA-L Ferrous fumarate Chemical compound [Fe+2].[O-]C(=O)\C=C\C([O-])=O PMVSDNDAUGGCCE-TYYBGVCCSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 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 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 2
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+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 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- JUJLDYVCLNLGTH-UHFFFAOYSA-N nickel;1,2,3,4-tetramethylcyclopentane Chemical compound [Ni].C[C]1[CH][C](C)[C](C)[C]1C.C[C]1[CH][C](C)[C](C)[C]1C JUJLDYVCLNLGTH-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- PZZICILSCNDOKK-UHFFFAOYSA-N propane-1,2,3-triamine Chemical compound NCC(N)CN PZZICILSCNDOKK-UHFFFAOYSA-N 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- ZXQVPEBHZMCRMC-UHFFFAOYSA-R tetraazanium;iron(2+);hexacyanide Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] ZXQVPEBHZMCRMC-UHFFFAOYSA-R 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
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- LGYODGULDSIGEB-UHFFFAOYSA-N iron(2+) 5-propan-2-ylcyclopenta-1,3-diene Chemical compound [Fe++].CC(C)[c-]1cccc1.CC(C)[c-]1cccc1 LGYODGULDSIGEB-UHFFFAOYSA-N 0.000 description 1
- ANAIULQUYDWKAL-UHFFFAOYSA-J iron(2+);disulfate Chemical compound [Fe+2].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ANAIULQUYDWKAL-UHFFFAOYSA-J 0.000 description 1
- VAPRHKOWFRYFTF-UHFFFAOYSA-N iron(2+);methanolate Chemical compound [Fe+2].[O-]C.[O-]C VAPRHKOWFRYFTF-UHFFFAOYSA-N 0.000 description 1
- AQBLLJNPHDIAPN-LNTINUHCSA-K iron(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Fe+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O AQBLLJNPHDIAPN-LNTINUHCSA-K 0.000 description 1
- QUHDSMAREWXWFM-UHFFFAOYSA-N iron(3+);propan-2-olate Chemical compound [Fe+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] QUHDSMAREWXWFM-UHFFFAOYSA-N 0.000 description 1
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 1
- LNOZJRCUHSPCDZ-UHFFFAOYSA-L iron(ii) acetate Chemical compound [Fe+2].CC([O-])=O.CC([O-])=O LNOZJRCUHSPCDZ-UHFFFAOYSA-L 0.000 description 1
- VRIVJOXICYMTAG-IYEMJOQQSA-L iron(ii) gluconate Chemical compound [Fe+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O VRIVJOXICYMTAG-IYEMJOQQSA-L 0.000 description 1
- SDTGEKAAGAIGJL-UHFFFAOYSA-N iron;1,2,3,4-tetramethylcyclopentane Chemical compound [Fe].C[C]1[CH][C](C)[C](C)[C]1C.C[C]1[CH][C](C)[C](C)[C]1C SDTGEKAAGAIGJL-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 1
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 229960005222 phenazone Drugs 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- KGRJUMGAEQQVFK-UHFFFAOYSA-L platinum(2+);dibromide Chemical compound Br[Pt]Br KGRJUMGAEQQVFK-UHFFFAOYSA-L 0.000 description 1
- CJWLZBLADIYQOV-UHFFFAOYSA-L platinum(2+);dinitrite Chemical compound [Pt+2].[O-]N=O.[O-]N=O CJWLZBLADIYQOV-UHFFFAOYSA-L 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- QFKMMXYLAPZKIB-UHFFFAOYSA-N undecan-1-amine Chemical compound CCCCCCCCCCCN QFKMMXYLAPZKIB-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Description
本発明は、窒素含有炭素材料に関する。 The present invention relates to a nitrogen-containing carbon material.
炭素材料は、従来、吸着材等として主に使用されていたが、導電性等の電子材料物性、高い熱伝導率、低い熱膨張率、軽さ、耐熱性等の基本的な性質を持つために幅広い用途が検討されるようになってきている。特に最近はその化学的機能に着目されて、リチウムイオン二次電池負極、キャパシタ用電極、固体高分子型燃料電池の電極、化学反応の触媒等の分野で検討されている。 Conventionally, carbon materials have been mainly used as adsorbents, etc., but they have basic properties such as physical properties of electronic materials such as conductivity, high thermal conductivity, low thermal expansion coefficient, lightness, and heat resistance. A wide range of applications has been studied. In particular, recently, attention has been paid to its chemical function, and studies have been made in the fields of lithium ion secondary battery negative electrode, capacitor electrode, polymer electrolyte fuel cell electrode, chemical reaction catalyst, and the like.
かかる炭素材料は、椰子殻、石炭コークス、石炭又は石油ピッチ、フラン樹脂、フェノール樹脂等を原料とし、炭化処理して製造されている。 Such a carbon material is manufactured by carbonization using coconut shell, coal coke, coal or petroleum pitch, furan resin, phenol resin, or the like as a raw material.
近年になって、かかる炭素材料に他の元素を含有させて炭素材料の物性の幅をさらに広げて発展させようとする試みがある。 In recent years, attempts have been made to further expand the range of physical properties of carbon materials by incorporating other elements into such carbon materials.
こうした中、最近は、窒素がドープされた炭素材料（以下、窒素含有炭素材料という）を用いて酸素還元活性を発現させて、固体高分子型燃料電池の電極や化学反応の触媒等に用いるという検討が進められている（例えば特許文献１）。 Under such circumstances, recently, a carbon material doped with nitrogen (hereinafter referred to as a nitrogen-containing carbon material) is used to develop oxygen reduction activity, which is used for an electrode of a polymer electrolyte fuel cell, a catalyst for a chemical reaction, or the like. Investigations are underway (for example, Patent Document 1).
しかし、いまだ窒素含有炭素材料の酸素還元等の活性は不十分である。
また窒素含有炭素材料を製造するには、特殊な出発物質を合成する必要があり、製造プロセスが複雑であったり、資源、エネルギーの消費が大きいという問題があり、製造コストも高くなるという問題がある。
However, the activity of the nitrogen-containing carbon material such as oxygen reduction is still insufficient.
In addition, in order to produce a nitrogen-containing carbon material, it is necessary to synthesize special starting materials, and there are problems that the production process is complicated, resources and energy are consumed, and that production costs are also high. is there.
本発明は、以上の状況を鑑み、化学反応の触媒、燃料電池の電極等の用途において、従来の窒素含有炭素材料と比較して、高い活性を有する窒素含有炭素材料を提供することを目的とする。 In view of the above situation, an object of the present invention is to provide a nitrogen-containing carbon material having a higher activity compared to conventional nitrogen-containing carbon materials in applications such as catalysts for chemical reactions and electrodes for fuel cells. To do.
また本発明は、従来の窒素含有炭素材料と比較して、エネルギーの消費が少なく製造プロセスが比較的簡易である製造方法を提供することを目的とする。 Another object of the present invention is to provide a production method that consumes less energy and has a relatively simple production process compared to conventional nitrogen-containing carbon materials.
本発明者は、上記課題を解決するために鋭意研究を重ねた結果、アズルミン酸と遷移金属を含むプレカーサーを炭化して得られる窒素含有炭素材料は、上記課題を解決できることを見出し、本発明をなすに至った。
すなわち、本発明は、下記のとおりである。
As a result of intensive studies to solve the above problems, the present inventor has found that a nitrogen-containing carbon material obtained by carbonizing a precursor containing azulmic acid and a transition metal can solve the above problems. It came to an eggplant.
That is, the present invention is as follows.
〔１〕[1]
炭素原子に対する窒素原子の原子数比（Ｎ／Ｃ）が０．０３〜０．６の窒素含有炭素材料であって、 A nitrogen-containing carbon material having an atomic ratio (N / C) of nitrogen atoms to carbon atoms of 0.03 to 0.6,
ＣｕＫα線をＸ線源として得られるＸ線回折図において、回折角（２θ）が２４．０〜２６．５°の位置にピークを有し、該ピークの半値幅が７．５°以下であって、 In an X-ray diffraction diagram obtained using CuKα rays as an X-ray source, the diffraction angle (2θ) has a peak at a position of 24.0 to 26.5 °, and the half width of the peak is 7.5 ° or less. And
Ｆｅ、Ｎｉ、及びＰｔからなる群より選ばれる少なくとも１種の遷移金属を含有する、 Containing at least one transition metal selected from the group consisting of Fe, Ni, and Pt,
窒素含有炭素材料。 Nitrogen-containing carbon material.
〔２〕[2]
前記遷移金属の含有量が、０．０１〜７０質量％である、前項〔１〕に記載の窒素含有炭素材料。 The nitrogen-containing carbon material according to [1], wherein the content of the transition metal is 0.01 to 70% by mass.
〔３〕[3]
炭素原子に対する窒素原子の原子数比（Ｎ／Ｃ）が０．０３〜０．６の窒素含有炭素材料であって、 A nitrogen-containing carbon material having an atomic ratio (N / C) of nitrogen atoms to carbon atoms of 0.03 to 0.6,
大気圧下２００Ｎｃｃ／ｍｉｎ．の窒素気流中で６０分かけて１０００℃まで昇温し、１０００℃で１時間保持した後、ＣｕＫα線をＸ線源として得られるＸ線回折図において、回折角（２θ）が２４．０〜２６．５°の位置にピークを有し、該ピークの半値幅が７．５°以下であって、 200 Ncc / min. Under atmospheric pressure. In an X-ray diffractogram obtained by using CuKα rays as an X-ray source after raising the temperature to 1000 ° C. over 60 minutes in a nitrogen stream and holding at 1000 ° C. for 1 hour, the diffraction angle (2θ) is 24.0. Having a peak at a position of 26.5 °, and the half width of the peak is 7.5 ° or less,
Ｆｅ、Ｎｉ、及びＰｔからなる群より選ばれる少なくとも１種の遷移金属を含有する、 Containing at least one transition metal selected from the group consisting of Fe, Ni, and Pt,
窒素含有炭素材料。 Nitrogen-containing carbon material.
〔４〕[4]
前記遷移金属の含有量が、０．０１〜７０質量％である、前項〔３〕に記載の窒素含有炭素材料。 The nitrogen-containing carbon material according to [3], wherein the content of the transition metal is 0.01 to 70% by mass.
本発明の窒素含有炭素材料は、燃料電池の電極として有用である。 The nitrogen-containing carbon material of the present invention is useful as a fuel cell electrode.
アズルミン酸とは、主として青酸を重合して得られる重合物の総称である。
図１は、窒素含有炭素材料を製造するための工程の一例を示す。図１に示すように、青酸を含む原料を重合してアズルミン酸を製造する工程Ｓ１０と、アズルミン酸と遷移金属を含むプレカーサーを製造する工程Ｓ１２と、炭化する工程Ｓ１４とを有する。
Azulmic acid is a general term for polymers obtained mainly by polymerizing hydrocyanic acid.
FIG. 1 shows an example of a process for producing a nitrogen-containing carbon material. As shown in FIG. 1, it has process S10 which manufactures the raw material containing hydrocyanic acid and manufactures azulmic acid, process S12 which manufactures the precursor containing azulmic acid and a transition metal, and carbonization process S14.
工程Ｓ１０で用いる青酸は、特に限定されず、公知の方法で製造されるものを用いることができる。具体的には、プロピレン、イソブチレン、ｔｅｒｔ−ブチルアルコール、プロパンまたはイソブタンを触媒存在下にアンモニア、酸素含有ガスと反応させる気相接触反応によってアクリロニトリルやメタクリロニトリルを製造する方法において副生されるものを用いることができる。このために工程Ｓ１０で用いる青酸は非常に安価に入手することが可能である。例えばメタノールのようにアンモ酸化反応によって青酸を生成するような原料を、アクリロニトリルやメタクリロニトリルの反応器に供給すると副生する青酸を増産することができる。 The cyanic acid used in step S10 is not particularly limited, and those produced by a known method can be used. Specifically, by-products are produced as a by-product in a process for producing acrylonitrile or methacrylonitrile by a gas phase catalytic reaction in which propylene, isobutylene, tert-butyl alcohol, propane or isobutane is reacted with ammonia or an oxygen-containing gas in the presence of a catalyst. Can be used. For this reason, the cyanuric acid used in step S10 can be obtained at a very low cost. For example, when a raw material such as methanol that generates hydrocyanic acid by an ammoxidation reaction is supplied to an acrylonitrile or methacrylonitrile reactor, the byproduct hydrocyanic acid can be increased.
また天然ガスの主成分であるメタンを触媒存在下にアンモニア、酸素含有ガスと反応させるアンドリュッソー法によって青酸を製造されることができる。この方法はメタンを原料とするために、非常に安価に青酸を入手できる方法である。 Further, hydrocyanic acid can be produced by an Andrewss method in which methane, which is a main component of natural gas, is reacted with ammonia and an oxygen-containing gas in the presence of a catalyst. Since this method uses methane as a raw material, it is a method by which hydrocyanic acid can be obtained at a very low cost.
もちろん青化ソーダ等を用いる実験室的な製造方法であってもかまわないが、コストの観点では上記の工業的に製造される青酸を用いるのが好ましい。 Of course, it may be a laboratory production method using sodium blue soda, but from the viewpoint of cost, it is preferable to use the above industrially produced cyanic acid.
工程Ｓ１２で用いるアズルミン酸は、特に限定されないが、主として青酸を含む原料を重合して得られる黒色〜黒褐色の青酸重合物である。青酸を含む原料において、青酸に対するその他の重合性物質の存在比は４０質量％以下であるのが好ましく、より好ましくは１０質量％以下であり、さらに好ましくは５質量％以下であり、特に好ましくは１質量％以下である。 アズルミン酸は、青酸を種々の方法で重合させることにより製造することができる。例えば液化青酸や青酸水溶液を加熱する方法、長時間放置する方法、塩基を添加する方法、光を照射する方法、高エネルギーの放射をする方法、種々の放電を行う方法や、シアン化カリウム水溶液の電気分解による方法が挙げられる。この他、文献にもアズルミン酸の重合方法の記載があり、例としてＡｎｇｅｗ．Ｃｈｅｍ．７２巻、３７９−３８４（１９６０年）及びその引用文献、並びに真空科学、１６巻、６４−７２（１９６９年）及びその引用文献が挙げられる。 The azulmic acid used in step S12 is not particularly limited, but is a black to black brown hydrocyanic acid polymer obtained by polymerizing a raw material mainly containing hydrocyanic acid. In the raw material containing hydrocyanic acid, the abundance ratio of the other polymerizable substance to hydrocyanic acid is preferably 40% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, and particularly preferably. 1% by mass or less. Azulmic acid can be produced by polymerizing hydrocyanic acid by various methods. For example, a method of heating liquefied hydrocyanic acid or aqueous hydrocyanic acid, a method of leaving for a long time, a method of adding a base, a method of irradiating light, a method of emitting high energy, a method of performing various discharges, electrolysis of an aqueous solution of potassium cyanide The method by is mentioned. In addition, there is a description of the polymerization method of azulmic acid in the literature, and Angew. Chem. 72, 379-384 (1960) and references cited therein, and vacuum science, 16, 64-72 (1969) and references cited therein.
塩基の存在下に青酸を重合させる方法において、塩基として、水酸化ナトリウム、水酸化カリウム、シアン化ナトリウム、シアン化カリウム、有機塩基、アンモニア、アンモニア水を例示することができる。有機塩基としては、一級アミンＲ1ＮＨ2、二級アミンＲ1Ｒ2ＮＨ、三級のアミンＲ1Ｒ2Ｒ3Ｎ、四級アンモニウム塩Ｒ1Ｒ2Ｒ3Ｒ4Ｎ+が一般的に用いられる（但し、Ｒ1〜Ｒ4は互いに同一又は異なってもよい炭素数１〜１０のアルキル基、フェニル基、ヘキシル基、およびこれらが結合して得られる基、である。Ｒ1〜Ｒ4に官能基を含んでよい。）。脂肪族又は環式脂肪族の第三級アミンが好ましい。例えば、トリメチルアミン、トリエチルアミン、トリプロピルアミン、トリブチルアミン、ジシクロヘキシルメチルアミン、テトラメチルアンモニウムヒドロキサイド、Ｎ−メチルピロリジン、１，８−ジアザビシクロ［５．４．０］ウンデク−７−エン（ＤＢＵ）を挙げることができる。青酸の重合方法のうち、重合段階で金属成分を含まないという観点で好ましいのは、液化青酸や青酸水溶液を加熱する、あるいは長時間放置する、光を照射する、高エネルギーの放射をする、アンモニア、有機塩基の存在下で重合する方法である。 In the method of polymerizing hydrocyanic acid in the presence of a base, examples of the base include sodium hydroxide, potassium hydroxide, sodium cyanide, potassium cyanide, organic base, ammonia, and aqueous ammonia. Examples of the organic base, primary amine R 1 NH 2, secondary amine R 1 R 2 NH, tertiary amine R 1 R 2 R 3 N, quaternary ammonium salt-free R 1 R 2 R 3 R 4 N + general manner are used (however, R 1 to R 4 is a group, obtained the same or different and an alkyl group having 1 to 10 carbon atoms, a phenyl group, a hexyl group, and then they are bonded to each other .R 1 ~ R 4 may contain a functional group). Aliphatic or cycloaliphatic tertiary amines are preferred. Examples include trimethylamine, triethylamine, tripropylamine, tributylamine, dicyclohexylmethylamine, tetramethylammonium hydroxide, N-methylpyrrolidine, 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU). be able to. Among the polymerization methods of cyanic acid, from the viewpoint of not containing a metal component in the polymerization step, it is preferable to heat liquefied hydrocyanic acid or an aqueous solution of hydrocyanic acid or leave it for a long time, irradiate light, emit high energy, ammonia The polymerization is carried out in the presence of an organic base.
また、プロピレン等のアンモ酸化工程で副生する青酸の精製工程において見られる装置の付着物から回収することによってもアズルミン酸を製造することができる。 Azulmic acid can also be produced by recovering from the deposits of the apparatus found in the purifying process of cyanuric acid by-produced in the ammoxidation process such as propylene.
アズルミン酸の組成は、ＣＨＮ分析計を用いて測定することができる。（窒素元素の質量％）／（炭素元素の質量％）は０．２〜１．０が好ましく、より好ましくは０．３〜０．９であり、特に好ましくは０．４〜０．９である。（水素元素の質量％）／（炭素元素の質量％）は０．０３〜０．２が好ましく、より好ましくは０．０５〜０．１５であり、特に好ましくは０．０８〜０．１１である。 The composition of azulmic acid can be measured using a CHN analyzer. (Mass% of nitrogen element) / (mass% of carbon element) is preferably 0.2 to 1.0, more preferably 0.3 to 0.9, and particularly preferably 0.4 to 0.9. is there. (Mass% of hydrogen element) / (mass% of carbon element) is preferably 0.03 to 0.2, more preferably 0.05 to 0.15, and particularly preferably 0.08 to 0.11. is there.
アズルミン酸は、波数１０００〜２０００ｃｍ-1のレーザーラマンスペクトル図において、ラマンシフトが１３００〜１４００ｃｍ-1、１５００〜１６００ｃｍ-1の位置にピークを持つことが好ましく、特に好ましくは１３６０〜１３８０ｃｍ-1、１５３０〜１５５０ｃｍ-1の位置にピークを持つ。 Azulmic acid, in the laser Raman spectrum of the wave number 1000～2000Cm -1, the Raman shift 1300～1400Cm -1, it is preferable to have a peak position of 1500～1600Cm -1, particularly preferably 1360～1380Cm -1, It has a peak at a position of 1530 to 1550 cm −1 .
アズルミン酸は、ＣｕＫα線をＸ線源として得られるＸ線回折図の１０〜５０°の範囲において、回折角（２θ）が２６．８±１°の位置に、好ましくは２６．８±０．５°の位置に、より好ましくは２６．８±０．２°の位置に強いピークを示す。また、前述のピークに加えて、本発明で用いるアズルミン酸は、ＣｕＫα線をＸ線源として得られるＸ線回折図の１０〜５０°の範囲において、回折角（２θ）が１２．３±１°の位置に、好ましくは１２．３±０．５°の位置にもピークを示す。 Azulmic acid has a diffraction angle (2θ) of 26.8 ± 1 °, preferably 26.8 ± 0. 0, in the range of 10 to 50 ° in the X-ray diffraction diagram obtained using CuKα rays as an X-ray source. A strong peak is shown at a position of 5 °, more preferably at a position of 26.8 ± 0.2 °. In addition to the above-mentioned peak, the azurmic acid used in the present invention has a diffraction angle (2θ) of 12.3 ± 1 in the range of 10 to 50 ° in the X-ray diffraction diagram obtained using CuKα rays as an X-ray source. A peak also appears at the position of °, preferably at the position of 12.3 ± 0.5 °.
次いで、アズルミン酸と遷移金属を含むプレカーサーを製造する（工程Ｓ１２）。アズルミン酸と遷移金属の原料とを溶媒中で混合し、次いで溶媒を除去することにより、プレカーサーを製造するのが好ましい。 Then, to produce a precursor containing a transition metal and azulmic acid (Step S 12). It is preferable to produce a precursor by mixing azulmic acid and the raw material of the transition metal in a solvent and then removing the solvent.
遷移金属としては、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｙ、Ｚｒ、Ｎｂ、Ｍｏ、Ｔｃ、Ｒｕ、Ｒｈ、Ｐｄ、Ａｇ、Ｔａ、Ｗ、Ｒｅ、Ｉｒ、Ｐｔ、Ａｕ、ランタノイド元素が好ましい。より好ましくは、Ｆｅ、Ｃｏ、Ｎｉ、Ｐｄ、Ｐｔ、Ａｕ、Ｌａ、Ｃｅであり、特に好ましくはＰｔ、Ｆｅ、Ｃｏ、Ｎｉである。 Transition metals include Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Ta, W, Re, Ir, Pt, Au A lanthanoid element is preferred. More preferable are Fe, Co, Ni, Pd, Pt, Au, La, and Ce, and particularly preferable are Pt, Fe, Co, and Ni.
遷移金属の原料としては、遷移金属のシュウ酸塩、水酸化物、酸化物、亜硝酸塩、硝酸
塩、酢酸塩、アンモニウム塩、炭酸塩、塩化物、臭化物、アルコキシド、アセチルアセト
ナート、フタロシアニン、ポルフィリン等を用いることができる。
鉄原料としては、鉄(II)フタロシアニン、鉄(III)アセチルアセトネート、鉄(II)メト
キシド、鉄(III)エトキシド、鉄(III)イソプロポキシド、ビス(シクロペンタジエニル)鉄
、ビス(エチルシクロペンタジエニル)鉄、ビス(イソプロピルシクロペンタジエニル)鉄、ビス(テトラメチルシクロペンタジエニル)鉄、塩化第二鉄、クエン酸第二鉄 、りん化第二鉄、酒石酸第二鉄、フマル酸第一鉄、 ヘキサシアノ鉄(II)酸アンモニウム、ヘキサシアノ鉄(II)酸アンモニウム鉄(III)、しゅう酸アンモニウム鉄(III)三水和物 、硫酸鉄(III)アンモニウム、硫酸アンモニウム鉄(III)、ビス(シクロペンタジエニル)鉄、塩化第二鉄、エチレンジアミン四酢酸、クエン酸鉄アンモニウム、硝酸第二鉄、酢酸鉄(II)、フマル酸鉄(II)、グルコン酸鉄(II) 、シュウ酸鉄及び水酸化鉄(III)を例示できる。好ましくは鉄(II)フタロシアニン、硝酸鉄である。
Transition metal raw materials include transition metal oxalate, hydroxide, oxide, nitrite, nitrate, acetate, ammonium salt, carbonate, chloride, bromide, alkoxide, acetylacetonate, phthalocyanine, porphyrin, etc. Can be used .
Iron raw materials include iron (II) phthalocyanine, iron (III) acetylacetonate, iron (II) methoxide, iron (III) ethoxide, iron (III) isopropoxide, bis (cyclopentadienyl) iron, bis ( Ethylcyclopentadienyl) iron , bis (isopropylcyclopentadienyl) iron, bis (tetramethylcyclopentadienyl) iron, ferric chloride, ferric citrate, ferric phosphide, ferric tartrate , Ferrous fumarate, ammonium hexacyanoferrate (II), ammonium hexacyanoferrate (II) ammonium iron (III), ammonium oxalate iron (III) trihydrate, iron (III) sulfate ammonium, iron iron sulfate (III ), Bis (cyclopentadienyl) iron, ferric chloride, ethylenediaminetetraacetic acid, ammonium iron citrate, ferric nitrate, iron (II) acetate, iron (II) fumarate, iron (II) gluconate, Iron oxalate and iron (III) hydroxide It can be illustrated. Iron (II) phthalocyanine and iron nitrate are preferred.
ニッケル原料としては、ニッケル(II)フタロシアニン、ニッケル(II)トリフルオロアセチルアセトナート、ビス(シクロペンタジエニル)ニッケル、ビス(イソプロピルシクロペンタジエニル)ニッケル ビス(ペンタメチルシクロペンタジエニル)ニッケル、ビス(テトラメチルシクロペンタジエニル)ニッケル、ほう酸ニッケルヒドロキシ酢酸ニッケル、ナフテン酸ニッケル、ビス(エチルシクロペンタジエニル)ニッケル、硫酸ニッケル(II)アンモニウム、ビス(1,5-シクロオクタジエン)ニッケル、ビス(テトラメチルシクロペンタジエニル)ニッケル、臭化ヘキサアンミンニッケル(II)、塩化ヘキサアンミンニッケル(II) 、酢酸ニッケル(II) 四水和物、アセチルアセトン酸ニッケル(II)、硫酸ニッケルアンモニウム、塩化ニッケル(II)、臭化ニッケル、炭酸ニッケル(II)、ぎ酸ニッケル(II)、ヘキサフルオロアセチルアセトナトニッケル(II)、酸化ニッケル(II)、ヒドロキシ酢酸ニッケル(II)、乳酸ニッケル(II)、硝酸ニッケル、しゅう酸ニッケル(II)、2,4-ペンタンジオン酸ニッケル(II)、硫酸ニッケル、アミド硫酸ニッケル、水酸化ニッケルを例示できる。好ましくは、ニッケル(II)フタロシアニン、硝酸ニッケルである。 Nickel raw materials include nickel (II) phthalocyanine, nickel (II) trifluoroacetylacetonate, bis (cyclopentadienyl) nickel, bis (isopropylcyclopentadienyl) nickel bis (pentamethylcyclopentadienyl) nickel, Bis (tetramethylcyclopentadienyl) nickel, nickel borate nickel hydroxyacetate nickel, naphthenic acid nickel, bis (ethylcyclopentadienyl) nickel, nickel (II) ammonium sulfate, bis (1,5-cyclooctadiene) nickel, Bis (tetramethylcyclopentadienyl) nickel, hexaamminenickel bromide (II) , hexaamminenickel (II) chloride, nickel (II) acetate tetrahydrate, nickel (II) acetylacetonate, nickel ammonium sulfate, chloride Nickel (II) , nickel bromide, nickel carbonate Le (II), formic acid nickel (II), hexafluoro acetylacetonate nickel (II), nickel oxide (II), hydroxyacetic acid nickel (II), lactic acid nickel (II), nickel nitrate, nickel oxalate (II) 2,4-pentanedioic acid nickel (II), nickel sulfate, amido nickel sulfate, and nickel hydroxide. Preferred are nickel (II) phthalocyanine and nickel nitrate.
コバルト原料としては、コバルト(II)フタロシアニン、コバルト(II)トリフルオロアセチルアセトナート、ビス(シクロペンタジエニル)コバルト、ビス(イソプロピルシクロペンタジエニル)コバルト、ビス(ペンタメチルシクロペンタジエニル)コバルト、ビス(テトラメチルシクロペンタジエニル)コバルト、ほう酸コバルトヒドロキシ酢酸コバルト、ナフテン酸コバルト、ビス(エチルシクロペンタジエニル)コバルト、硫酸コバルト(II)アンモニウム、ビス(1,5-シクロオクタジエン)コバルト、ビス(テトラメチルシクロペンタジエニル)コバルト、臭化ヘキサアンミンコバルト(II)、塩化ヘキサアンミンコバルト(II) 、酢酸コバルト(II) 四水和物、アセチルアセトン酸コバルト(II)、硫酸コバルトアンモニウム、塩化コバルト(II)、臭化コバルト、炭酸コバルト(II)、ぎ酸コバルト(II)、ヘキサフルオロアセチルアセトナトコバルト(II)、酸化コバルト(II)、ヒドロキシ酢酸コバルト(II)、乳酸コバルト(II)、ナフテン酸ニッケル(II)、硝酸コバルト、しゅう酸コバルト(II)、2,4-ペンタンジオン酸コバルト(II)、硫酸コバルト、アミド硫酸コバルト、水酸化コバルトを例示できる。好ましくは、コバルト(II)フタロシアニン、硝酸コバルトである。 Cobalt raw materials include cobalt (II) phthalocyanine, cobalt (II) trifluoroacetylacetonate, bis (cyclopentadienyl) cobalt, bis (isopropylcyclopentadienyl) cobalt , bis (pentamethylcyclopentadienyl) cobalt , Bis (tetramethylcyclopentadienyl) cobalt, cobalt borate hydroxycobalt cobalt acetate, cobalt naphthenate, bis (ethylcyclopentadienyl) cobalt, cobalt (II) ammonium sulfate, bis (1,5-cyclooctadiene) cobalt , Bis (tetramethylcyclopentadienyl) cobalt, hexaamminecobalt bromide (II) , hexaamminecobalt (II) chloride, cobalt (II) acetate tetrahydrate, cobalt (II) acetylacetonate, cobaltammonium sulfate, cobalt chloride (II), cobalt bromide, carbonate Koba (II), cobalt formate (II), hexafluoroacetylacetonato cobalt (II), cobalt (II) oxide, cobalt (II) hydroxyacetate, cobalt (II) lactate, nickel (II) naphthenate, cobalt nitrate And cobalt (II) oxalate, cobalt (II) 2,4-pentandionate, cobalt sulfate, cobalt amidosulfate, and cobalt hydroxide. Preferred are cobalt (II) phthalocyanine and cobalt nitrate.
白金原料としては、白金(II)アセチルアセトナート、ヘキサブロモ白金酸(IV)アンモニウム、ヘキサクロロ白金(IV)酸アンモニウム、テトラクロロ白金(II)酸アンモニウム、ビス(アセチルアセトナート)白金(II)、ビス(エチレンジアミン)白金(II)クロリド、クロロ白金酸六水和物、ジクロロジアンミン白金(II)、テトラクロロジアンミン白金(IV)、1,1-シクロブタンジカルボシラトジアンミン白金(II)、ジアンミンジクロロ白金(II)、亜硝酸ジアンミン白金(II)、ジクロロビス(ベンゾニトリル)白金(II)、ヘキサクロロ白金酸(IV)二水素、ヘキサブロモ白金酸(IV)二水素、ヘキサヒドロオクソ白金酸(IV)、ジフェニル(1,5-シクロオクタジエン)白金(II)、ヘキサヒドロキソ白金(IV)酸、臭化白金(II)、塩化白金(II)、ヘキサフルオロアセチルアセトン酸白金(II)、塩化テトラアンミン白金(II)、炭酸水素テトラアンミン白金(II)、テトラアンミン白金(II)水酸化物、硝酸テトラアミン白金 (II)、テトラアミン白金(II)テトラクロロ白金(II)酸及びヘキサヒドロキソ白金硝酸水溶液を例示できる。 Platinum raw materials include platinum (II) acetylacetonate, ammonium hexabromoplatinate (IV), ammonium hexachloroplatinate (IV), ammonium tetrachloroplatinate (II), bis (acetylacetonato) platinum (II), bis (Ethylenediamine) platinum (II) chloride, chloroplatinic acid hexahydrate , dichlorodiammine platinum (II), tetrachlorodiammine platinum (IV), 1,1-cyclobutanedicarbosilatodiammine platinum (II), diammine dichloroplatinum ( II), diammine platinum nitrite (II), dichlorobis (benzonitrile) platinum (II), hexachloroplatinic acid (IV) dihydrogen, hexabromoplatinic acid (IV) dihydrogen, hexahydrooxoplatinic acid (IV) , diphenyl ( 1,5-cyclooctadiene) platinum (II), hexahydroxoplatinum (IV) acid, platinum (II) bromide, platinum (II) chloride, platinum (II) hexafluoroacetylacetonate, tetrachloride Examples include ammineplatinum (II) , tetraammineplatinum hydrogen carbonate (II) , tetraammineplatinum (II) hydroxide, tetraamineplatinum (II) nitrate, tetraamineplatinum (II) tetrachloroplatinum (II) acid and hexahydroxoplatinum nitrate aqueous solution. it can.
溶媒としては、アズルミン酸との親和性が高い溶媒が好ましい。有機溶媒、水、水溶液を例示できる。極性溶媒の方が、アズルミン酸との親和性が高い傾向がある。 As the solvent, a solvent having high affinity with azulmic acid is preferable. An organic solvent, water, and aqueous solution can be illustrated. Polar solvents tend to have higher affinity with azulmic acid.
有機溶媒としては、極性溶媒が好ましい。クロロホルム、酢酸エチル、テトラヒドロフラン、塩化メチレン、アセトン、アセトニトリル、N,N-ジメチルホルムアミド、ジメチルスルホキシド、酢酸、1-ブタノール、2-プロパノール、1-プロパノール、エタノール、メタノール、ギ酸、アミノ基を有する溶媒を例示できる。アミノ基を有する溶媒として、第一級アミンを例示することができる。具体的には、アミノ基を有する溶媒として、アンモニア、メチルアミン、エチルアミン、プロピルアミン、イソプロピルアミン、ブチルアミン、アミルアミン、ヘキシルアミン、ヘプチルアミン、オクチルアミン、ノニルアミン、デシルアミン、ウンデシルアミン、ドデシルアミン、トリデシルアミン、テトラデシルアミン、ペンタデシルアミン、セチルアミン、シクロプロピルアミン、シクロブチルアミン、シクロペンチルアミン、シクロヘキシルアミン、アニリン、トルイジン、ベンジルアミン、ナフチルアミン、アリルアミン等のモノアミン、エチレンジアミン、トリメチレンジアミン、テトラメチレンジアミン、ペンタメチレンジアミン、ヘキサメチレンジアミン、１，７−ジアミノヘプタン、１，８−ジアミノオクタン、１，９−ジアミノノナン、１，１０−ジアミノデカン、フェニレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンエキサミン等のジアミン、１，２，３−トリアミノプロパン、トリアミノベンゼン、トリアミノフェノール、メラミン等のトリアミンを例示できる。 As the organic solvent, a polar solvent is preferable. Chloroform, ethyl acetate, tetrahydrofuran, methylene chloride, acetone, acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, acetic acid, 1-butanol, 2-propanol, 1-propanol, ethanol, methanol, formic acid, solvents with amino groups It can be illustrated. A primary amine can be illustrated as a solvent which has an amino group. Specifically, examples of solvents having amino groups include ammonia, methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, Decylamine, tetradecylamine, pentadecylamine, cetylamine, cyclopropylamine , cyclobutylamine, cyclopentylamine, cyclohexylamine, aniline, toluidine, benzylamine, naphthylamine, allylamine and other monoamines, ethylenediamine, trimethylenediamine, tetramethylenediamine, Pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9- Aminonane, 1,10-diaminodecane, phenylenediamine, diethylenetriamine, triethylenetetramine, diamine such as tetraethylenepentamine, pentaethyleneexamine, 1,2,3-triaminopropane, triaminobenzene, triaminophenol, melamine And the like.
これらの中で、エチレンジアミン、トリメチレンジアミン、テトラメチレンジアミン、１，２，３−トリアミノプロパンが好ましく、エチレンジアミンがより好ましい。 Among these, ethylenediamine, trimethylenediamine, tetramethylenediamine, and 1,2,3-triaminopropane are preferable, and ethylenediamine is more preferable.
塩基性水溶液としては、例えば、第一級アミンの水溶液、アルカリ金属の水溶液、アルカリ土類金属の水溶液、４級アンモニウム塩の水溶液等を例示することができる。第一級アミンの水溶液としては、アンモニア水溶液、メチルアミン水溶液、エチルアミン水溶液、プロピルアミン水溶液、イソプロピルアミン水溶液、ブチルアミン水溶液、アミルアミン水溶液、ヘキシルアミン水溶液の等のモノアミン水溶液、エチレンジアミン水溶液、トリメチレンジアミン水溶液、テトラメチレンジアミン水溶液等のジアミン水溶液、メラミン水溶液等のトリアミン水溶液を例示できる。アルカリ金属の水溶液としては水酸化ナトリウム水溶液、水酸化カリウム水溶液等を、アルカリ土類金属の水溶液としては水酸化カルシウム水溶液、水酸化バリウム水溶液等を、４級アンモニウム塩の水溶液としてはテトラメチルアンモニウムヒドロキシド水溶液、テトラエチルアンモニウムヒドロキシド水溶液、テトラプロピルアンモニウムヒドロキシド水溶液、テトラブチルアンモニウムヒドロキシド水溶液等を例示することができる。これらの中で、好ましくはアンモニア水溶液、水酸化ナトリウム水溶液、水酸化カリウム水溶液、テトラエチルアンモニウムヒドロキシド水溶液である。 Examples of the basic aqueous solution include an aqueous solution of a primary amine, an aqueous solution of an alkali metal, an aqueous solution of an alkaline earth metal, an aqueous solution of a quaternary ammonium salt, and the like. As an aqueous solution of primary amine, aqueous ammonia solution, aqueous solution of methylamine, aqueous solution of ethylamine, aqueous solution of propylamine, aqueous solution of isopropylamine, aqueous solution of butylamine, aqueous solution of amylamine, aqueous solution of hexylamine, aqueous solution of ethylenediamine, aqueous solution of trimethylenediamine, Examples include diamine aqueous solutions such as tetramethylene diamine aqueous solutions and triamine aqueous solutions such as melamine aqueous solutions. Sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, etc. as alkaline metal aqueous solution, calcium hydroxide aqueous solution, barium hydroxide aqueous solution etc. as alkaline earth metal aqueous solution, tetramethylammonium hydroxy as aqueous solution of quaternary ammonium salt Aqueous solution of aqueous solution, aqueous solution of tetraethylammonium hydroxide, aqueous solution of tetrapropylammonium hydroxide, aqueous solution of tetrabutylammonium hydroxide and the like. Among these, an aqueous ammonia solution, an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, and an aqueous tetraethylammonium hydroxide solution are preferable.
酸性水溶液として、硫酸水溶液、硝酸水溶液、塩酸水溶液、燐酸水溶液を例示することができる。これらの中で、好ましくは硫酸水溶液である。 Examples of the acidic aqueous solution include a sulfuric acid aqueous solution, a nitric acid aqueous solution, a hydrochloric acid aqueous solution, and a phosphoric acid aqueous solution. Among these, a sulfuric acid aqueous solution is preferable.
アズルミン酸と遷移金属の原料の比率は限定されないが、好ましくはアズルミン酸に対して遷移金属の原料は０．００１以上であり、より好ましくは０．００５以上であり、特に好ましくは０．０１以上である。またアズルミン酸に対して遷移金属の原料は１０以下であり、より好ましくは１以下であり、特に好ましくは０．１以下である。 The ratio of the raw materials of azulmic acid and transition metal is not limited, but preferably the raw material of transition metal with respect to azulmic acid is 0.001 or more, more preferably 0.005 or more, and particularly preferably 0.01 or more. It is. Moreover, the raw material of a transition metal with respect to azulmic acid is 10 or less, More preferably, it is 1 or less, Most preferably, it is 0.1 or less.
溶媒との混合に先立って、アズルミン酸は予めボールミル等で粉砕しておくことが好ましい。 Prior to mixing with the solvent, it is preferable to pulverize the azulmic acid in advance with a ball mill or the like.
アズルミン酸と溶媒の混合比率は、溶解性、希釈したい比率、混合方法に応じて決めればよい。アズルミン酸に対して質量比で１〜１００００倍、好ましくは１０〜１００倍を例示できる。質量比が低いと溶解性が悪く、高いと溶媒の除去のために消費するエネルギーが増える。 What is necessary is just to determine the mixing ratio of an azulmic acid and a solvent according to solubility, the ratio to dilute, and a mixing method. Examples thereof include 1 to 10,000 times, preferably 10 to 100 times by mass ratio with respect to azulmic acid. If the mass ratio is low, the solubility is poor, and if it is high, the energy consumed for removing the solvent increases.
溶媒の種類によってはアズルミン酸と反応する可能性もあるが、全体として溶解した状態になる限り、反応していても差し支えない。すなわち、溶液又は不溶物を含む混合液中に、アズルミン酸と溶媒の少なくとも一部が反応したものを含む態様を経由する窒素含有炭素材料の製造方法も、本実施形態の範疇である。また水等の溶媒中で青酸を重合することによってアズルミン酸を得ることができるが、生成したアズルミン酸を含む溶液又は不溶物を含む混合液をプレカーサーの製造に利用することもできる。生成したアズルミン酸は難溶性の場合が多いが、酸及び／又は塩基を添加する等によって、溶解状態にすることも可能である。 Although it may react with azulmic acid depending on the type of solvent, it may be reacted as long as it is in a dissolved state as a whole. That is, a method for producing a nitrogen-containing carbon material through an embodiment in which at least a part of azulmic acid and a solvent is reacted in a mixed solution containing a solution or an insoluble material is also included in the category of this embodiment. In addition, azurmic acid can be obtained by polymerizing hydrocyanic acid in a solvent such as water. However, a solution containing azulmic acid produced or a mixed solution containing insoluble matter can also be used for the production of a precursor. The produced azulmic acid is often poorly soluble, but it can be made into a dissolved state by adding an acid and / or a base.
アズルミン酸と溶媒を混合する温度は特に限定されないが、溶媒の融点以上かつ溶媒の沸点若しくは分解温度以下が好ましい。混合時間としては、１分間〜１００時間を例示できる。好ましくは１０分から２０時間であり、より好ましくは３０分から２時間である。混合中は振とうしたり攪拌したり超音波をかけたりすることが好ましい。 The temperature at which azulmic acid and the solvent are mixed is not particularly limited, but is preferably not lower than the melting point of the solvent and not higher than the boiling point or decomposition temperature of the solvent. Examples of the mixing time include 1 minute to 100 hours. It is preferably 10 minutes to 20 hours, more preferably 30 minutes to 2 hours. During mixing, it is preferable to shake, stir or apply ultrasonic waves.
溶媒を除去する方法としては、常圧あるいは減圧下で加熱して溶媒を除去する方法、噴霧乾燥させる方法を例示できる。 Examples of the method for removing the solvent include a method for removing the solvent by heating under normal pressure or reduced pressure, and a method for spray drying.
工程Ｓ１４について説明する。
炭化の方法は、以下のものに限定されないが、回転炉、トンネル炉、管状炉、流動焼成炉等を用い、プレカーサーを不活性ガス雰囲気下で５００〜１５００℃、好ましくは６００〜１２００℃、より好ましくは７００〜１１００℃、特に好ましくは、８００〜１０００℃の範囲で熱処理することにより行うことができる。上記不活性ガスとしては、以下のガスに限定されないが、例えば窒素、アルゴン、ヘリウム、ネオン、二酸化炭素等の不活性ガスが挙げられ、コスト的には窒素ガスが好ましい。なお、不活性ガス雰囲気で熱処理する代わりに、真空中で熱処理しても良い。
Step S14 will be described.
The method of carbonization is not limited to the following, but using a rotary furnace, tunnel furnace, tubular furnace, fluidized firing furnace, etc., the precursor is 500 to 1500 ° C., preferably 600 to 1200 ° C. in an inert gas atmosphere. Preferably, it can be carried out by heat treatment in the range of 700 to 1100 ° C, particularly preferably in the range of 800 to 1000 ° C. The inert gas is not limited to the following gas, but includes, for example, an inert gas such as nitrogen, argon, helium, neon, carbon dioxide, and nitrogen gas is preferable in terms of cost. In addition, you may heat-process in a vacuum instead of heat-processing in inert gas atmosphere.
不活性ガス雰囲気で炭化する場合、不活性ガスは静止していても流通していてもよいが、流通しているのが好ましい。窒素含有炭素材料の酸化を防ぐ観点で、不活性ガス中の酸素濃度は５％以下が好ましく、より好ましくは１％以下であり、特に好ましくは１０００ｐｐｍ以下である。炭化処理時間としては１０秒〜１００時間、好ましくは５分〜１０時間、より好ましくは１５分〜５時間、さらにより好ましくは３０分〜２時間の範囲である。炭化工程の圧力は、０．０１〜５ＭＰａ、好ましくは０．０５〜１ＭＰａ、より好ましくは０．０８〜０．３ＭＰａ、特に好ましくは、０．０９〜０．１５ＭＰａである。高圧処理はｓｐ３軌道によって構成されるダイヤモンド構造となるために好ましくない。 When carbonizing in an inert gas atmosphere, the inert gas may be stationary or distributed, but is preferably distributed. From the viewpoint of preventing oxidation of the nitrogen-containing carbon material, the oxygen concentration in the inert gas is preferably 5% or less, more preferably 1% or less, and particularly preferably 1000 ppm or less. The carbonization time is in the range of 10 seconds to 100 hours, preferably 5 minutes to 10 hours, more preferably 15 minutes to 5 hours, and even more preferably 30 minutes to 2 hours. The pressure in the carbonization step is 0.01 to 5 MPa, preferably 0.05 to 1 MPa, more preferably 0.08 to 0.3 MPa, and particularly preferably 0.09 to 0.15 MPa. The high-pressure treatment is not preferable because it has a diamond structure composed of sp3 orbitals.
窒素含有炭素材料は、触媒や電極用途には平均粒子径（体積基準のメディアン径：５０％Ｄ）が０．１μｍ以上１００μｍ以下であることが好ましく、０．５μｍ以上３０μｍ以下であることがより好ましい。また触媒や電極用途向けにはＢＥＴ法により測定した比表面積は、３０〜２５００ｍ2／ｇの範囲内にすることが好ましい。比表面積が３０ｍ2／ｇ未満であれば活性が低く、２５００ｍ2／ｇを超えるものは、合成が難しい、からである。ＢＥＴ法により測定した比表面積のさらに好ましい範囲は、５０〜６００ｍ2／ｇである。 The nitrogen-containing carbon material preferably has an average particle diameter (volume-based median diameter: 50% D) of 0.1 μm or more and 100 μm or less, and more preferably 0.5 μm or more and 30 μm or less for catalyst and electrode applications. preferable. For catalyst and electrode applications, the specific surface area measured by the BET method is preferably in the range of 30 to 2500 m 2 / g. The specific surface area is less active is less than 30 m 2 / g, in excess of 2500 m 2 / g, the synthesis is difficult, is from. A more preferable range of the specific surface area measured by the BET method is 50 to 600 m 2 / g.
得られた窒素含有炭素材料中の遷移金属の含有量は、０．０１〜７０質量％の範囲内にすることが望ましい。より好ましい範囲は、０．１〜５０質量％であり、特に好ましくは０．５〜８％である。 The content of the transition metal in the obtained nitrogen-containing carbon material is desirably in the range of 0.01 to 70% by mass. A more preferable range is 0.1 to 50% by mass, and particularly preferably 0.5 to 8%.
なお、工程Ｓ１４で得られた窒素含有炭素材料を後処理することもできる。後処理としては粉砕、溶媒による洗浄、再焼成が挙げられる。洗浄用の溶媒としては酸性水溶液を例示できる。 Note that the nitrogen-containing carbon material obtained in step S14 can be post-treated. Post-processing includes pulverization, washing with a solvent, and re-firing. As the solvent for washing, an acidic aqueous solution can be exemplified.
本実施態様の窒素含有炭素材料は、
（１）炭素原子に対する窒素原子の原子数比（Ｎ／Ｃ）が０．０３〜０．６、
（２）ＣｕＫα線をＸ線源として得られるＸ線回折図において、回折角（２θ）が２４．０〜２６．５°の位置にピークを有し、該ピークの半値幅が７．５°以下、
である。
The nitrogen-containing carbon material of this embodiment is
(1) The atomic ratio (N / C) of nitrogen atoms to carbon atoms is 0.03 to 0.6,
(2) In an X-ray diffraction diagram obtained using CuKα rays as an X-ray source, the diffraction angle (2θ) has a peak at a position of 24.0 to 26.5 °, and the half width of the peak is 7.5 °. Less than,
It is.
好ましくは（Ｎ／Ｃ）が０．０４以上、より好ましくは０．０５以上、特に好ましくは０．０６以上である。好ましくは（Ｎ／Ｃ）が０．５以下、より好ましくは０．４以下、特に好ましくは０．３以下である。 (N / C) is preferably 0.04 or more, more preferably 0.05 or more, and particularly preferably 0.06 or more. (N / C) is preferably 0.5 or less, more preferably 0.4 or less, and particularly preferably 0.3 or less.
好ましくは回折角（２θ）が２５．０〜２６．４°の位置に、より好ましくは、２５．４〜２６．３°の位置に、特に好ましくは２５．６〜２６．１°の位置に、ピークを有する。好ましくは該ピークの半値幅が７°以下であり、より好ましくは６°以下であり、特に好ましくは５°以下である。好ましくは該ピークの半値幅が０．００１°以上であり、より好ましくは０．０１°以上であり、特に好ましくは０．０４°以上である。 Preferably, the diffraction angle (2θ) is at a position of 25.0 to 26.4 °, more preferably at a position of 25.4 to 26.3 °, and particularly preferably at a position of 25.6 to 26.1 ° . Have a peak. Preferably, the full width at half maximum of the peak is 7 ° or less, more preferably 6 ° or less, and particularly preferably 5 ° or less. The full width at half maximum of the peak is preferably 0.001 ° or more, more preferably 0.01 ° or more, and particularly preferably 0.04 ° or more.
なお上述のＸ線回折ピークを示さない窒素含有炭素材料についても、高温で再焼成した後に、２４．０〜２６．５°の位置に７．５°以下の半値幅を有するピークを示すものであれば、本実施態様の窒素含有炭素材料の範疇である。 The nitrogen-containing carbon material that does not show the above X-ray diffraction peak also shows a peak having a half-value width of 7.5 ° or less at a position of 24.0 to 26.5 ° after re-baking at a high temperature. If there is, it is a category of the nitrogen-containing carbon material of the present embodiment.
すなわち、窒素含有炭素材料の試験片を作製し、これを大気圧下２００Ｎｃｃ／ｍｉｎ．の窒素気流中で６０分かけて１０００℃まで昇温し、１０００℃で１時間ホールド（保持）した後、ＣｕＫα線をＸ線源としてＸ線回折図を得る。このＸ線回折図において、回折角（２θ）が２４．０〜２６．５°の位置にピークを有し、該ピークの半値幅が７．５°以下であるものは、本実施態様の窒素含有炭素材料である。 That is, a test piece of nitrogen-containing carbon material was prepared, and this was tested at 200 Ncc / min. The temperature is raised to 1000 ° C. over 60 minutes in a nitrogen stream and held (held) at 1000 ° C. for 1 hour, and then an X-ray diffraction diagram is obtained using CuKα rays as an X-ray source. In this X-ray diffraction pattern, the diffraction angle (2θ) has a peak at a position of 24.0 to 26.5 °, and the half width of the peak is 7.5 ° or less. It is a contained carbon material.
したがって、製造履歴の不明な窒素含有炭素材料についてＸ線回折ピークを調べる場合、（再焼成しない状態で）試験片のＸ線回折を測定して所定のピークを示さないときは、サンプルを大気圧下２００Ｎｃｃ／ｍｉｎ．の窒素気流中で６０分かけて１０００℃まで昇温し、１０００℃で１時間ホールド（保持）した後のＸ線回折ピークも調べるのが好ましい。
Therefore, when examining the X-ray diffraction peak of a nitrogen-containing carbon material whose production history is unknown, when the X-ray diffraction of the test piece is measured (without recalcination) and does not show a predetermined peak, the sample is taken to atmospheric pressure.
本実施態様の窒素含有炭素材料は、化学反応の触媒、固体高分子型燃料電池の電極、金属―空気電池の電極等に用いることができる。アズルミン酸の原料としてはアクリロニトリル等基礎原料の製造において、プロピレンやプロパン等の原料が反応する際に副生物として得られる青酸が利用可能である。青酸を熱処理して製造されるアズルミン酸から窒素含有炭素材料を製造する方法は、工程数が少なく、比較的高い収率である。よって省資源、省エネルギーに窒素含有炭素材料を製造する方法と言える。従って、燃料電池の電極及びこの電極を用いて得られる燃料電池に利用する場合も、効率的且つ安価で、しかも省資源、省エネルギーで製造することができ、工業上非常に有用である。 The nitrogen-containing carbon material of this embodiment can be used as a catalyst for chemical reaction, an electrode of a polymer electrolyte fuel cell, an electrode of a metal-air cell, and the like. As a raw material of azulmic acid, hydrocyanic acid obtained as a by-product when a raw material such as propylene or propane reacts in the production of a basic raw material such as acrylonitrile can be used. The method for producing a nitrogen-containing carbon material from azulmic acid produced by heat treating cyanic acid has a small number of steps and a relatively high yield. Therefore, it can be said that it is a method for producing a nitrogen-containing carbon material in order to save resources and energy. Therefore, even when used for an electrode of a fuel cell and a fuel cell obtained by using this electrode, it can be manufactured efficiently and inexpensively with resource saving and energy saving, and is very useful industrially.
以下に本発明の実施例等を挙げて本発明をさらに詳細に説明するが、これらは例示的なものであり、本発明は以下の具体例に制限されるものではない。当業者は以下に示す実施例に様々な変更を加えて本発明を実施することができ、かかる変更は本願の特許請求の範囲に包含される。
分析方法は以下のとおりとした。
EXAMPLES The present invention will be described in more detail below with reference to examples and the like of the present invention, but these are illustrative and the present invention is not limited to the following specific examples. Those skilled in the art can implement the present invention by making various modifications to the examples described below, and such modifications are included in the scope of the claims of the present application.
The analysis method was as follows.
＜分析方法＞
（ＣＨＮ分析）
ジェイサイエンスラボ社製ＭＩＣＲＯ ＣＯＲＤＥＲ ＪＭ１０を用い、２５００μｇの試料を試料台に充填してＣＨＮ分析を行った。試料炉は９５０℃、燃焼炉（酸化銅触媒）は８５０℃、還元炉（銀粒＋酸化銅のゾーン、還元銅のゾーン、酸化銅のゾーンからなる）は５５０℃に設定されている。酸素は１５ｍｌ／ｍｉｎ、Ｈｅは１５０ｍｌ／ｍｉｎに設定されている。検出器はＴＣＤである。アンチピリン（Ａｎｔｉｐｙｒｉｎｅ）を用いてマニュアルに記載の方法でキャリブレーションを行う。
<Analysis method>
(CHN analysis)
Using a MICRO CORDER JM10 manufactured by J Science Lab Inc., a sample of 2500 μg was filled in a sample stage and subjected to CHN analysis. The sample furnace is set to 950 ° C., the combustion furnace (copper oxide catalyst) is set to 850 ° C., and the reduction furnace (consisting of a silver grain + copper oxide zone, a reduced copper zone, and a copper oxide zone) is set to 550 ° C. Oxygen is set to 15 ml / min and He is set to 150 ml / min. The detector is a TCD. Calibration is performed by the method described in the manual using antipyrine.
（金属量の分析）
ＸＲＦ（リガク ＲＩＸ−３０００、Ｘ線管球：Ｒｈ管球、管電圧：５０ｋＶ、管電流５０ｍＡ）を用いて定量分析を行い、窒素含有炭素材料中に含まれる金属量を定量した。
(Analysis of metal content)
Quantitative analysis was performed using XRF (Rigaku RIX-3000, X-ray tube: Rh tube, tube voltage: 50 kV, tube current 50 mA), and the amount of metal contained in the nitrogen-containing carbon material was quantified.
（Ｘ線回折の測定）
Ｘ線回折パターンは、試料をメノウ乳鉢で粉砕後、粉末用セルに充填して下記の条件で測定した。装置：リガク社製Ｒｉｎｔ２５００、Ｘ線管球：Ｃｕ管球（Ｃｕ−Ｋα線） 管電圧：４０ｋＶ、管電流：２００ｍＡ、分光結晶：あり、散乱スリット：１°、発散スリット：１°、受光スリット：０．１５ｍｍ、スキャン速度：２°／分、サンプリング幅：０．０２°、スキャン法：２θ／θ法。Ｘ線回折角（２θ）の補正は、シリコン粉末について得られたＸ線回折角データを用いて行った。
(Measurement of X-ray diffraction)
The X-ray diffraction pattern was measured under the following conditions after pulverizing the sample with an agate mortar and filling the powder cell. Apparatus: Rint 2500 manufactured by Rigaku Corporation, X-ray tube: Cu tube (Cu-Kα ray) Tube voltage: 40 kV, tube current: 200 mA, spectral crystal: Yes, scattering slit: 1 °, diverging slit: 1 °, light receiving slit : 0.15 mm, scan speed: 2 ° / min, sampling width: 0.02 °, scan method: 2θ / θ method. The X-ray diffraction angle (2θ) was corrected using the X-ray diffraction angle data obtained for the silicon powder.
＜アズルミン酸の製造例＞
水３５０ｇに青酸１５０ｇを溶解させた水溶液を調製し、攪拌を行いながら、２５％アンモニア水溶液１２０ｇを１０分かけて添加し、得られた混合液を３５℃に加熱した。重合が始まり黒褐色の重合物が析出し始め、温度は徐々に上昇し４５℃となった。２時間後から３０質量％青酸水溶液を２００ｇ／ｈの速度で添加し、４時間かけて８００ｇ添加した。添加中は反応温度５０℃保つようにコントロールした。この温度で１００時間攪拌した。得られた黒色沈殿物をろ過によって分離し、黒色のアズルミン酸を得た。このときの収率は９６％であった。分離後の沈殿物を水洗した後、乾燥器にて１２０℃で４時間乾燥させてアズルミン酸を得た。
<Production example of azulmic acid>
An aqueous solution in which 150 g of hydrocyanic acid was dissolved in 350 g of water was prepared, 120 g of 25% aqueous ammonia solution was added over 10 minutes while stirring, and the resulting mixture was heated to 35 ° C. Polymerization started and a blackish brown polymer started to precipitate, and the temperature gradually increased to 45 ° C. After 2 hours, a 30% by mass aqueous solution of hydrocyanic acid was added at a rate of 200 g / h, and 800 g was added over 4 hours. During the addition, the reaction temperature was controlled to be kept at 50 ° C. Stir at this temperature for 100 hours. The resulting black precipitate was separated by filtration to obtain black azulmic acid. The yield at this time was 96%. The separated precipitate was washed with water and then dried at 120 ° C. for 4 hours in a drier to obtain azulmic acid.
［実施例１］
＜窒素含有炭素材料の製造＞
硝酸鉄（ＩＩＩ）・９水和物０．７ｇを純水２０ｇに溶解させて硝酸鉄水溶液を調製した。アズルミン酸１０ｇを２５％アンモニア水２００ｇと混合して５０℃で１時間加熱したのちに硝酸鉄水溶液を添加し、そのまま５０℃で１時間攪拌してプレカーサー混合液を得た。プレカーサー混合液を、ロータリーエバポレーターにて２００ｒｐｍで回転させながら、減圧下で溶媒を蒸発させて、プレカーサーを得た。得られたプレカーサーを内径２５ｍｍの石英管に充填し、大気圧下、２００Ｎｃｃ／ ｍｉｎ．の窒素気流中で６０分かけて８００℃まで昇温させ、８００℃で１時間ホールドすることにより炭化させ３ｇの窒素含有炭素材料を得た。
[Example 1]
<Manufacture of nitrogen-containing carbon materials>
An aqueous iron nitrate solution was prepared by dissolving 0.7 g of iron (III) nitrate nonahydrate in 20 g of pure water. After 10 g of azulmic acid was mixed with 200 g of 25% aqueous ammonia and heated at 50 ° C. for 1 hour, an aqueous iron nitrate solution was added, and stirred at 50 ° C. for 1 hour to obtain a precursor mixture. The precursor was obtained by evaporating the solvent under reduced pressure while rotating the precursor mixture at 200 rpm with a rotary evaporator. The obtained precursor was filled into a quartz tube having an inner diameter of 25 mm, and 200 Ncc / min. In a nitrogen stream, the temperature was raised to 800 ° C. over 60 minutes and carbonized by holding at 800 ° C. for 1 hour to obtain 3 g of a nitrogen-containing carbon material.
＜窒素含有炭素材料の解析＞
（ＣＨＮ分析結果）
ＣＨＮ分析より、炭素原子に対する窒素原子の原子数比（Ｎ／Ｃ）を分析した。結果を表１に示す。
（金属量の分析結果）
結果を表１に示す。
<Analysis of nitrogen-containing carbon materials>
(CHN analysis results)
From CHN analysis, the ratio of the number of nitrogen atoms to carbon atoms (N / C) was analyzed. The results are shown in Table 1.
(Analysis result of metal content)
The results are shown in Table 1.
＜電極作製＞
得られた窒素含有炭素材料を粉砕、分級して平均粒径約１０μｍ（日機装社製Ｍｉｃｒｏｔｒａｃ ＭＴ３３００）として電極作製に用いた。
窒素含有炭素材料の粉末５ｍｇに精製水を加え５ｇに調整し、超音波を印加して分散させ、０．１％触媒懸濁液を得た。この触媒懸濁液を回転ディスクカーボン電極上に１２０μｌ滴下し、乾燥機において１２０℃で乾燥させた。次に導電性樹脂溶液（アシプレックス、旭化成ケミカルズ登録商標、含有量０．１５％エタノール溶液）を９０μｌ滴下し、同じく乾燥機において１２０℃で約２時間乾燥させ、触媒試験電極を作製した。
<Electrode production>
The obtained nitrogen-containing carbon material was pulverized and classified to obtain an average particle size of about 10 μm (Microtrac MT3300 manufactured by Nikkiso Co., Ltd.), which was used for electrode production.
Purified water was added to 5 mg of the nitrogen-containing carbon material powder to adjust to 5 g, and ultrasonic waves were applied to disperse to obtain a 0.1% catalyst suspension. 120 μl of this catalyst suspension was dropped on a rotating disk carbon electrode and dried at 120 ° C. in a dryer. Next, 90 μl of a conductive resin solution (Aciplex, Asahi Kasei Chemicals registered trademark, ethanol solution with a content of 0.15%) was dropped, and dried in a dryer at 120 ° C. for about 2 hours to prepare a catalyst test electrode.
＜電気化学的測定＞
白金線を対極、銀／塩化銀電極を参照極とした。酸性溶液中での酸素還元活性を調べるために、０．５Ｍの硫酸水溶液を使用した。この硫酸水溶液を純酸素で酸素飽和にするために１時間バブリングを行った。
次に、作用極を＋０．８Ｖから＋０Ｖの電位まで２ｍＶ／ｓｅｃで掃引し、電位−電流曲線を測定した。電位が０．５Ｖのときの電流を表１に示す。
<Electrochemical measurement>
A platinum wire was used as a counter electrode, and a silver / silver chloride electrode as a reference electrode. In order to investigate the oxygen reduction activity in an acidic solution, a 0.5 M aqueous sulfuric acid solution was used. In order to make this sulfuric acid aqueous solution oxygen saturated with pure oxygen, bubbling was performed for 1 hour.
Next, the working electrode was swept from +0.8 V to +0 V at 2 mV / sec, and a potential-current curve was measured. Table 1 shows currents when the potential is 0.5V.
［実施例２］
＜窒素含有炭素材料の製造＞
鉄（ＩＩ）フタロシアニン０．９ｇをエチレンジアミン２０ｇに溶解させてエチレンジアミン溶液を調製した。アズルミン酸１０ｇをエチレンジアミン２００ｇと混合して９０℃で１時間加熱したのちにエチレンジアミン溶液を添加し、そのまま９０℃で１時間攪拌してプレカーサー混合液を得た。プレカーサー混合液を、ロータリーエバポレーターにて２００ｒｐｍで回転させながら、減圧下で溶媒を蒸発させて、プレカーサーを得た。得られたプレカーサーを内径２５ｍｍの石英管に充填し、大気圧下、２００Ｎｃｃ／ ｍｉｎ．の窒素気流中で６０分かけて８００℃まで昇温させ、８００℃で１時間ホールドして炭化処理をして３ｇの窒素含有炭素材料を得た。
[Example 2]
<Manufacture of nitrogen-containing carbon materials>
An ethylenediamine solution was prepared by dissolving 0.9 g of iron (II) phthalocyanine in 20 g of ethylenediamine. After mixing 10 g of azulmic acid with 200 g of ethylenediamine and heating at 90 ° C. for 1 hour, the ethylenediamine solution was added and stirred at 90 ° C. for 1 hour to obtain a precursor mixture. The precursor was obtained by evaporating the solvent under reduced pressure while rotating the precursor mixture at 200 rpm with a rotary evaporator. The obtained precursor was filled into a quartz tube having an inner diameter of 25 mm, and 200 Ncc / min. In a nitrogen stream, the temperature was raised to 800 ° C. over 60 minutes, held at 800 ° C. for 1 hour and carbonized to obtain 3 g of a nitrogen-containing carbon material.
＜窒素含有炭素材料の解析＞
（ＣＨＮ分析結果）
ＣＨＮ分析より、炭素原子に対する窒素原子の原子数比（Ｎ／Ｃ）を分析した。結果を表１に示す。
（金属量の分析結果）
結果を表１に示す。
<Analysis of nitrogen-containing carbon materials>
(CHN analysis results)
From CHN analysis, the ratio of the number of nitrogen atoms to carbon atoms (N / C) was analyzed. The results are shown in Table 1.
(Analysis result of metal content)
The results are shown in Table 1.
＜窒素含有炭素材料の粉砕と分級＞
実施例１の粉砕と分級と同様に実施した。
＜電極作製＞
実施例１の電極作製と同様にして作製した。
＜電気化学的測定＞
実施例１の電気化学的測定と同様にして測定した。結果を表１に示す。
<Crushing and classification of nitrogen-containing carbon materials>
It carried out similarly to the grinding | pulverization and classification of Example 1.
<Electrode production>
It was produced in the same manner as the electrode production in Example 1.
<Electrochemical measurement>
The measurement was performed in the same manner as the electrochemical measurement in Example 1. The results are shown in Table 1.
［実施例３］
＜窒素含有炭素材料の製造＞
硝酸ニッケル（ＩＩ）・６水和物０．７ｇを純水２０ｇに溶解させて硝酸ニッケル水溶液を調製した。アズルミン酸１０ｇを２５％アンモニア水２００ｇと混合して５０℃で１時間加熱したのちに硝酸ニッケル水溶液を添加し、そのまま５０℃で１時間攪拌してプレカーサー混合液を得た。プレカーサー混合液を、ロータリーエバポレーターにて２００ｒｐｍで回転させながら、減圧下で溶媒を蒸発させて、プレカーサーを得た。得られたプレカーサーを内径２５ｍｍの石英管に充填し、大気圧下、２００Ｎｃｃ／ ｍｉｎ．の窒素気流中で６０分かけて８００℃まで昇温させ、８００℃で１時間ホールドして炭化処理をして３ｇの窒素含有炭素材料を得た。
[Example 3]
<Manufacture of nitrogen-containing carbon materials>
A nickel nitrate aqueous solution was prepared by dissolving 0.7 g of nickel (II) nitrate hexahydrate in 20 g of pure water. After mixing 10 g of azulmic acid with 200 g of 25% aqueous ammonia and heating at 50 ° C. for 1 hour, an aqueous nickel nitrate solution was added and stirred at 50 ° C. for 1 hour to obtain a precursor mixture. The precursor was obtained by evaporating the solvent under reduced pressure while rotating the precursor mixture at 200 rpm with a rotary evaporator. The obtained precursor was filled into a quartz tube having an inner diameter of 25 mm, and 200 Ncc / min. In a nitrogen stream, the temperature was raised to 800 ° C. over 60 minutes, held at 800 ° C. for 1 hour and carbonized to obtain 3 g of a nitrogen-containing carbon material.
＜窒素含有炭素材料の解析＞
（ＣＨＮ分析結果）
ＣＨＮ分析より、炭素原子に対する窒素原子の原子数比（Ｎ／Ｃ）を分析した。結果を表１に示す。
（金属量の分析結果）
結果を表１に示す。
<Analysis of nitrogen-containing carbon materials>
(CHN analysis results)
From CHN analysis, the ratio of the number of nitrogen atoms to carbon atoms (N / C) was analyzed. The results are shown in Table 1.
(Analysis result of metal content)
The results are shown in Table 1.
＜窒素含有炭素材料の粉砕と分級＞
実施例１の粉砕と分級と同様に実施した。
＜電極作製＞
実施例１の電極作製と同様にして作製した。
＜電気化学的測定＞
実施例１の電気化学的測定と同様にして測定した。結果を表１に示す。
<Crushing and classification of nitrogen-containing carbon materials>
It carried out similarly to the grinding | pulverization and classification of Example 1.
<Electrode production>
It was produced in the same manner as the electrode production in Example 1.
<Electrochemical measurement>
The measurement was performed in the same manner as the electrochemical measurement in Example 1. The results are shown in Table 1.
［実施例４］
＜窒素含有炭素材料の製造＞
ニッケル（ＩＩ）フタロシアニン０．９ｇをエチレンジアミン２０ｇに溶解させてエチレンジアミン溶液を調製した。アズルミン酸１０ｇをエチレンジアミン２００ｇと混合して９０℃で１時間加熱したのちにエチレンジアミン溶液を添加し、そのまま９０℃で１時間攪拌してプレカーサー混合液を得た。プレカーサー混合液を、ロータリーエバポレーターにて２００ｒｐｍで回転させながら、減圧下で溶媒を蒸発させて、プレカーサーを得た。得られたプレカーサーを内径２５ｍｍの石英管に充填し、大気圧下、２００Ｎｃｃ／ ｍｉｎ．の窒素気流中で６０分かけて８００℃まで昇温させ、８００℃で１時間ホールドして炭化処理をして３ｇの窒素含有炭素材料を得た。
[Example 4]
<Manufacture of nitrogen-containing carbon materials>
An ethylenediamine solution was prepared by dissolving 0.9 g of nickel (II) phthalocyanine in 20 g of ethylenediamine. After mixing 10 g of azulmic acid with 200 g of ethylenediamine and heating at 90 ° C. for 1 hour, the ethylenediamine solution was added and stirred at 90 ° C. for 1 hour to obtain a precursor mixture. The precursor was obtained by evaporating the solvent under reduced pressure while rotating the precursor mixture at 200 rpm with a rotary evaporator. The obtained precursor was filled into a quartz tube having an inner diameter of 25 mm, and 200 Ncc / min. In a nitrogen stream, the temperature was raised to 800 ° C. over 60 minutes, held at 800 ° C. for 1 hour and carbonized to obtain 3 g of a nitrogen-containing carbon material.
＜窒素含有炭素材料の解析＞
（ＣＨＮ分析結果）
ＣＨＮ分析より、炭素原子に対する窒素原子の原子数比（Ｎ／Ｃ）を分析した。結果を表１に示す。
（金属量の分析結果）
結果を表１に示す。
<Analysis of nitrogen-containing carbon materials>
(CHN analysis results)
From CHN analysis, the ratio of the number of nitrogen atoms to carbon atoms (N / C) was analyzed. The results are shown in Table 1.
(Analysis result of metal content)
The results are shown in Table 1.
＜窒素含有炭素材料の粉砕と分級＞
実施例１の粉砕と分級と同様に実施した。
＜電極作製＞
実施例１の電極作製と同様にして作製した。
＜電気化学的測定＞
実施例１の電気化学的測定と同様にして測定した。結果を表１に示す。
<Crushing and classification of nitrogen-containing carbon materials>
It carried out similarly to the grinding | pulverization and classification of Example 1.
<Electrode production>
It was produced in the same manner as the electrode production in Example 1.
<Electrochemical measurement>
The measurement was performed in the same manner as the electrochemical measurement in Example 1. The results are shown in Table 1.
［実施例５］
＜窒素含有炭素材料の製造＞
硝酸コバルト（ＩＩ）・６水和物０．７ｇを純水２０ｇに溶解させて硝酸コバルト水溶液を調製した。アズルミン酸１０ｇを２５％アンモニア水２００ｇと混合して５０℃で１時間加熱したのちに硝酸コバルト水溶液を添加し、そのまま５０℃で１時間攪拌してプレカーサー混合液を得た。プレカーサー混合液を、ロータリーエバポレーターにて２００ｒｐｍで回転させながら、減圧下で溶媒を蒸発させて、プレカーサーを得た。得られたプレカーサーを内径２５ｍｍの石英管に充填し、大気圧下、２００Ｎｃｃ／ ｍｉｎ．の窒素気流中で６０分かけて８００℃まで昇温させ、８００℃で１時間ホールドして炭化処理をして３ｇの窒素含有炭素材料を得た。
[Example 5]
<Manufacture of nitrogen-containing carbon materials>
A cobalt nitrate aqueous solution was prepared by dissolving 0.7 g of cobalt (II) nitrate hexahydrate in 20 g of pure water. After mixing 10 g of azulmic acid with 200 g of 25% aqueous ammonia and heating at 50 ° C. for 1 hour, an aqueous cobalt nitrate solution was added, and the mixture was stirred as it was at 50 ° C. for 1 hour to obtain a precursor mixture. The precursor was obtained by evaporating the solvent under reduced pressure while rotating the precursor mixture at 200 rpm with a rotary evaporator. The obtained precursor was filled into a quartz tube having an inner diameter of 25 mm, and 200 Ncc / min. In a nitrogen stream, the temperature was raised to 800 ° C. over 60 minutes, held at 800 ° C. for 1 hour and carbonized to obtain 3 g of a nitrogen-containing carbon material.
＜窒素含有炭素材料の解析＞
（ＣＨＮ分析結果）
ＣＨＮ分析より、炭素原子に対する窒素原子の原子数比（Ｎ／Ｃ）を分析した。結果を表１に示す。
（金属量の分析結果）
結果を表１に示す。
<Analysis of nitrogen-containing carbon materials>
(CHN analysis results)
From CHN analysis, the ratio of the number of nitrogen atoms to carbon atoms (N / C) was analyzed. The results are shown in Table 1.
(Analysis result of metal content)
The results are shown in Table 1.
＜窒素含有炭素材料の粉砕と分級＞
実施例１の粉砕と分級と同様に実施した。
＜電極作製＞
実施例１の電極作製と同様にして作製した。
＜電気化学的測定＞
実施例１の電気化学的測定と同様にして測定した。結果を表１に示す。
<Crushing and classification of nitrogen-containing carbon materials>
It carried out similarly to the grinding | pulverization and classification of Example 1.
<Electrode production>
It was produced in the same manner as the electrode production in Example 1.
<Electrochemical measurement>
The measurement was performed in the same manner as the electrochemical measurement in Example 1. The results are shown in Table 1.
[実施例６]
アズルミン酸１０ｇを２５％アンモニア水２００ｇと混合して５０℃で１時間加熱した
のちに白金を０．０１ｇ含むヘキサヒドロキソ白金酸水溶液を添加し、そのまま５０℃
で１時間攪拌してプレカーサー混合液を得た。プレカーサー混合液を、ロータリーエバポ
レーターにて２００ｒｐｍで回転させながら、減圧下で溶媒を蒸発させて、プレカーサー
を得た。得られたプレカーサーを内径２５ｍｍの石英管に充填し、
大気圧下、２００Ｎｃｃ/ ｍｉｎ．の１０％水素ガス中（窒素９０％）で４００℃で２時
間ホールドし、ついで大気圧下、２００Ｎｃｃ/ ｍｉｎ．の窒素気流中で６０分かけて８
００℃まで昇温させ、８００℃で１時間ホールドして炭化処理をして３ｇの窒素含有炭素
材料を得た。
[Example 6]
After mixing 10 g of azulmic acid with 200 g of 25% aqueous ammonia and heating at 50 ° C. for 1 hour, an aqueous hexahydroxoplatinic acid solution containing 0.01 g of platinum was added, and the temperature was kept at 50 ° C.
And stirred for 1 hour to obtain a precursor mixture. The precursor was obtained by evaporating the solvent under reduced pressure while rotating the precursor mixture at 200 rpm with a rotary evaporator. Fill the resulting precursor into a quartz tube with an inner diameter of 25 mm,
Under atmospheric pressure, 200 Ncc / min. In 10% hydrogen gas (90% nitrogen) at 400 ° C. for 2 hours and then 200 Ncc / min. 8 minutes over 60 minutes in a nitrogen stream
The temperature was raised to 00 ° C., held at 800 ° C. for 1 hour, and carbonized to obtain 3 g of a nitrogen-containing carbon material.
＜窒素含有炭素材料の解析＞
（ＣＨＮ分析結果）
ＣＨＮ分析より、炭素原子に対する窒素原子の原子数比（Ｎ／Ｃ）を分析した。結果を表１に示す。
（金属量の分析結果）
結果を表１に示す。
<Analysis of nitrogen-containing carbon materials>
(CHN analysis results)
From CHN analysis, the ratio of the number of nitrogen atoms to carbon atoms (N / C) was analyzed. The results are shown in Table 1.
(Analysis result of metal content)
The results are shown in Table 1.
＜窒素含有炭素材料の粉砕と分級＞
実施例１の粉砕と分級と同様に実施した。
＜電極作製＞
実施例１の電極作製と同様にして作製した。
＜電気化学的測定＞
実施例１の電気化学的測定と同様にして測定した。結果を表１に示す。
<Crushing and classification of nitrogen-containing carbon materials>
It carried out similarly to the grinding | pulverization and classification of Example 1.
<Electrode production>
It was produced in the same manner as the electrode production in Example 1.
<Electrochemical measurement>
The measurement was performed in the same manner as the electrochemical measurement in Example 1. The results are shown in Table 1.
［比較例１］
＜窒素含有炭素材料の製造＞
アズルミン酸１０ｇを内径２５ｍｍの石英管に充填し、大気圧下、２００Ｎｃｃ／ ｍｉｎ．の窒素気流中で６０分かけて８００℃まで昇温させ、８００℃で１時間ホールドして炭化処理をして３．４ｇの窒素含有炭素材料を得た。
[Comparative Example 1]
<Manufacture of nitrogen-containing carbon materials>
A quartz tube having an inner diameter of 25 mm was filled with 10 g of azulmic acid, and 200 Ncc / min. In a nitrogen stream, the temperature was raised to 800 ° C. over 60 minutes, held at 800 ° C. for 1 hour and carbonized to obtain 3.4 g of a nitrogen-containing carbon material.
＜窒素含有炭素材料の解析＞
（ＣＨＮ分析結果）
ＣＨＮ分析より、炭素原子に対する窒素原子の原子数比（Ｎ／Ｃ）を分析した。結果を表１に示す。
（金属量の分析結果）
結果を表１に示す。
<Analysis of nitrogen-containing carbon materials>
(CHN analysis results)
From CHN analysis, the ratio of the number of nitrogen atoms to carbon atoms (N / C) was analyzed. The results are shown in Table 1.
(Analysis result of metal content)
The results are shown in Table 1.
＜窒素含有炭素材料の粉砕と分級＞
実施例１の粉砕と分級と同様に実施した。
＜電極作製＞
実施例１の電極作製と同様にして作製した。
＜電気化学的測定＞
実施例１の電気化学的測定と同様にして測定した。結果を表１に示す。
<Crushing and classification of nitrogen-containing carbon materials>
It carried out similarly to the grinding | pulverization and classification of Example 1.
<Electrode production>
It was produced in the same manner as the electrode production in Example 1.
<Electrochemical measurement>
The measurement was performed in the same manner as the electrochemical measurement in Example 1. The results are shown in Table 1.
［比較例２］
＜窒素含有炭素材料の製造＞
硝酸鉄（ＩＩＩ）・９水和物０．７ｇを純水２０ｇに溶解させて硝酸鉄水溶液を調製した。比較例１と同様にして窒素含有炭素材料を得て、得られた窒素含有炭素材料３ｇを２５％アンモニア水２００ｇと混合して５０℃で１時間加熱したのちに硝酸鉄水溶液を添加し、そのまま５０℃で１時間攪拌してプレカーサー混合液を得た。プレカーサー混合液を、ロータリーエバポレーターにて２００ｒｐｍで回転させながら、減圧下で溶媒を蒸発させて、プレカーサーを得た。得られたプレカーサーを内径２５ｍｍの石英管に充填し、大気圧下、２００Ｎｃｃ／ ｍｉｎ．の窒素気流中で６０分かけて８００℃まで昇温させ、８００℃で１時間ホールドして炭化処理をして２．９ｇの窒素含有炭素材料を得た。
[Comparative Example 2]
<Manufacture of nitrogen-containing carbon materials>
An aqueous iron nitrate solution was prepared by dissolving 0.7 g of iron (III) nitrate nonahydrate in 20 g of pure water. A nitrogen-containing carbon material was obtained in the same manner as in Comparative Example 1, 3 g of the obtained nitrogen-containing carbon material was mixed with 200 g of 25% ammonia water and heated at 50 ° C. for 1 hour, and then an iron nitrate aqueous solution was added and left as it was. The mixture was stirred at 50 ° C. for 1 hour to obtain a precursor mixture. The precursor was obtained by evaporating the solvent under reduced pressure while rotating the precursor mixture at 200 rpm with a rotary evaporator. The obtained precursor was filled into a quartz tube having an inner diameter of 25 mm, and 200 Ncc / min. In a nitrogen stream, the temperature was raised to 800 ° C. over 60 minutes, held at 800 ° C. for 1 hour, and carbonized to obtain 2.9 g of a nitrogen-containing carbon material.
＜窒素含有炭素材料の解析＞
（ＣＨＮ分析結果）
ＣＨＮ分析より、炭素原子に対する窒素原子の原子数比（Ｎ／Ｃ）を分析した。結果を表１に示す。
（金属量の分析結果）
結果を表１に示す。
<Analysis of nitrogen-containing carbon materials>
(CHN analysis results)
From CHN analysis, the ratio of the number of nitrogen atoms to carbon atoms (N / C) was analyzed. The results are shown in Table 1.
(Analysis result of metal content)
The results are shown in Table 1.
＜窒素含有炭素材料の粉砕と分級＞
実施例１の粉砕と分級と同様に実施した。
＜電極作製＞
実施例１の電極作製と同様にして作製した。
＜電気化学的測定＞
実施例１の電気化学的測定と同様にして測定した。結果を表１に示す。
<Crushing and classification of nitrogen-containing carbon materials>
It carried out similarly to the grinding | pulverization and classification of Example 1.
<Electrode production>
It was produced in the same manner as the electrode production in Example 1.
<Electrochemical measurement>
The measurement was performed in the same manner as the electrochemical measurement in Example 1. The results are shown in Table 1.
比較例３においては、アズルミン酸以外では、窒素含有炭素材料の前駆体として最も窒素含有量の多い樹脂であるメラミン樹脂を用いた。 In Comparative Example 3, a melamine resin, which is a resin having the highest nitrogen content, was used as a precursor of a nitrogen-containing carbon material other than azulmic acid.
［比較例３］
＜メラミン樹脂の製造＞
メラミン２５２ｇと３７％ホルムアルデヒド水溶液６５０ｍＬを混合し、攪拌しながら６ｍｏｌ／Ｌの水酸化カリウム水溶液を少量加えて、ｐＨ８〜９にした。還流させながら、７０℃で攪拌して４０時間重合させた。この間、適宜水酸化カリウム水溶液を加えてｐＨを８〜９に保つようにした。５０時間後に加熱を停止し冷却し、１５００ｇの水を添加して反応液から分離してきた粘調な樹脂を取り出し、８０℃で真空乾燥させてメラミン樹脂を得た。
[Comparative Example 3]
<Manufacture of melamine resin>
252 g of melamine and 650 mL of 37% formaldehyde aqueous solution were mixed, and a small amount of 6 mol / L potassium hydroxide aqueous solution was added while stirring to adjust the pH to 8-9. While refluxing, the mixture was stirred at 70 ° C. for polymerization for 40 hours. During this time, an aqueous potassium hydroxide solution was appropriately added to maintain the pH at 8-9. After 50 hours, the heating was stopped and cooled, and 1500 g of water was added to remove the viscous resin separated from the reaction solution, followed by vacuum drying at 80 ° C. to obtain a melamine resin.
＜窒素含有炭素材料の製造＞
硝酸鉄（ＩＩＩ）・９水和物０．７ｇを純水２０ｇに溶解させて硝酸鉄水溶液を調製した。メラミン樹脂１０ｇを２５％アンモニア水２００ｇと混合して５０℃で１時間加熱したのちに硝酸鉄水溶液を添加し、そのまま５０℃で１時間攪拌してプレカーサー混合液を得た。プレカーサー混合液を、ロータリーエバポレーターにて２００ｒｐｍで回転させながら、減圧下で溶媒を蒸発させて、プレカーサーを得た。得られたプレカーサーを内径２５ｍｍの石英管に充填し、大気圧下、２００Ｎｃｃ／ ｍｉｎ．の窒素気流中で６０分かけて８００℃まで昇温させ、８００℃で１時間ホールドして炭化処理をして１．１ｇの窒素含有炭素材料を得た。
<Manufacture of nitrogen-containing carbon materials>
An aqueous iron nitrate solution was prepared by dissolving 0.7 g of iron (III) nitrate nonahydrate in 20 g of pure water. 10 g of melamine resin was mixed with 200 g of 25% aqueous ammonia and heated at 50 ° C. for 1 hour, and then an aqueous iron nitrate solution was added and stirred at 50 ° C. for 1 hour to obtain a precursor mixture. The precursor was obtained by evaporating the solvent under reduced pressure while rotating the precursor mixture at 200 rpm with a rotary evaporator. The obtained precursor was filled into a quartz tube having an inner diameter of 25 mm, and 200 Ncc / min. In a nitrogen stream, the temperature was raised to 800 ° C. over 60 minutes, held at 800 ° C. for 1 hour and carbonized to obtain 1.1 g of a nitrogen-containing carbon material.
＜窒素含有炭素材料の解析＞
（ＣＨＮ分析結果）
ＣＨＮ分析より、炭素原子に対する窒素原子の原子数比（Ｎ／Ｃ）を分析した。結果を表１に示す。
（金属量の分析結果）
結果を表１に示す。
<Analysis of nitrogen-containing carbon materials>
(CHN analysis results)
From CHN analysis, the ratio of the number of nitrogen atoms to carbon atoms (N / C) was analyzed. The results are shown in Table 1.
(Analysis result of metal content)
The results are shown in Table 1.
＜窒素含有炭素材料の粉砕と分級＞
実施例１の粉砕と分級と同様に実施した。
＜電極作成＞
実施例１の電極作製と同様にして作製した。
＜電気化学的測定＞
実施例１の電気化学的測定と同様にして測定した。結果を表１に示す。
<Crushing and classification of nitrogen-containing carbon materials>
It carried out similarly to the grinding | pulverization and classification of Example 1.
<Electrode creation>
It was produced in the same manner as the electrode production in Example 1.
<Electrochemical measurement>
The measurement was performed in the same manner as the electrochemical measurement in Example 1. The results are shown in Table 1.
［実施例７］
＜窒素含有炭素材料の製造＞
実施例１において硝酸鉄（ＩＩＩ）・９水和物０．７ｇを１．４ｇに、８００℃の焼成温度を１０００℃に変更した以外は実施例１を反復して２．６ｇの窒素含有炭素材料を得た。
[Example 7]
<Manufacture of nitrogen-containing carbon materials>
Example 1 was repeated except that 0.7 g of iron (III) nitrate nonahydrate was changed to 1.4 g and the firing temperature at 800 ° C. was changed to 1000 ° C. in Example 1. 2.6 g of nitrogen-containing carbon Obtained material.
＜窒素含有炭素材料の解析＞
（ＣＨＮ分析結果）
ＣＨＮ分析より、炭素原子に対する窒素原子の原子数比（Ｎ／Ｃ）を分析した。結果を表１に示す。
（金属量の分析結果）
結果を表１に示す。
<Analysis of nitrogen-containing carbon materials>
(CHN analysis results)
From CHN analysis, the ratio of the number of nitrogen atoms to carbon atoms (N / C) was analyzed. The results are shown in Table 1.
(Analysis result of metal content)
The results are shown in Table 1.
＜窒素含有炭素材料の粉砕と分級＞
実施例１の粉砕と分級と同様に実施した。
＜電極作製＞
実施例１の電極作製と同様にして作製した。
＜電気化学的測定＞
実施例１の電気化学的測定と同様にして測定した。結果を表１に示す。
<Crushing and classification of nitrogen-containing carbon materials>
It carried out similarly to the grinding | pulverization and classification of Example 1.
<Electrode production>
It was produced in the same manner as the electrode production in Example 1.
<Electrochemical measurement>
The measurement was performed in the same manner as the electrochemical measurement in Example 1. The results are shown in Table 1.
［実施例８］
＜窒素含有炭素材料の製造＞
実施例２において鉄（ＩＩ）フタロシアニン０．９ｇを１．４ｇに、８００℃の焼成温度を１０００℃に変更した以外は実施例２を反復して２．６ｇの窒素含有炭素材料を得た。
[Example 8]
<Manufacture of nitrogen-containing carbon materials>
Example 2 was repeated except that 0.9 g of iron (II) phthalocyanine was changed to 1.4 g and the firing temperature at 800 ° C. was changed to 1000 ° C. to obtain 2.6 g of a nitrogen-containing carbon material.
＜窒素含有炭素材料の解析＞
（ＣＨＮ分析結果）
ＣＨＮ分析より、炭素原子に対する窒素原子の原子数比（Ｎ／Ｃ）を分析した。結果を表１に示す。
（金属量の分析結果）
結果を表１に示す。
<Analysis of nitrogen-containing carbon materials>
(CHN analysis results)
From CHN analysis, the ratio of the number of nitrogen atoms to carbon atoms (N / C) was analyzed. The results are shown in Table 1.
(Analysis result of metal content)
The results are shown in Table 1.
＜窒素含有炭素材料の粉砕と分級＞
実施例１の粉砕と分級と同様に実施した。
＜電極作製＞
実施例１の電極作製と同様にして作製した。
＜電気化学的測定＞
実施例１の電気化学的測定と同様にして測定した。結果を表１に示す。
<Crushing and classification of nitrogen-containing carbon materials>
It carried out similarly to the grinding | pulverization and classification of Example 1.
<Electrode production>
It was produced in the same manner as the electrode production in Example 1.
<Electrochemical measurement>
The measurement was performed in the same manner as the electrochemical measurement in Example 1. The results are shown in Table 1.
［実施例９］
＜窒素含有炭素材料の製造＞
実施例３において硝酸ニッケル（ＩＩ）・６水和物０．７ｇを１ｇに、８００℃の焼成温度を１０００℃に変更した以外は実施例３を反復して２．６ｇの窒素含有炭素材料を得た。
[Example 9]
<Manufacture of nitrogen-containing carbon materials>
Example 3 was repeated except that 0.7 g of nickel (II) nitrate hexahydrate was changed to 1 g and the firing temperature at 800 ° C. was changed to 1000 ° C. to obtain 2.6 g of a nitrogen-containing carbon material. Obtained.
＜窒素含有炭素材料の解析＞
（ＣＨＮ分析結果）
ＣＨＮ分析より、炭素原子に対する窒素原子の原子数比（Ｎ／Ｃ）を分析した。結果を表１に示す。
（金属量の分析結果）
結果を表１に示す。
<Analysis of nitrogen-containing carbon materials>
(CHN analysis results)
From CHN analysis, the ratio of the number of nitrogen atoms to carbon atoms (N / C) was analyzed. The results are shown in Table 1.
(Analysis result of metal content)
The results are shown in Table 1.
＜窒素含有炭素材料の粉砕と分級＞
実施例１の粉砕と分級と同様に実施した。
＜電極作製＞
実施例１の電極作製と同様にして作製した。
＜電気化学的測定＞
実施例１の電気化学的測定と同様にして測定した。結果を表１に示す。
<Crushing and classification of nitrogen-containing carbon materials>
It carried out similarly to the grinding | pulverization and classification of Example 1.
<Electrode production>
It was produced in the same manner as the electrode production in Example 1.
<Electrochemical measurement>
The measurement was performed in the same manner as the electrochemical measurement in Example 1. The results are shown in Table 1.
［実施例１０］
＜窒素含有炭素材料の製造＞
実施例４においてニッケル（ＩＩ）フタロシアニン０．９ｇを１ｇに、８００℃の焼成温度を１０００℃に変更した以外は実施例４を反復して２．６ｇの窒素含有炭素材料を得た。
[Example 10]
<Manufacture of nitrogen-containing carbon materials>
Example 4 was repeated except that 0.9 g of nickel (II) phthalocyanine was changed to 1 g and the firing temperature at 800 ° C. was changed to 1000 ° C. to obtain 2.6 g of a nitrogen-containing carbon material.
＜窒素含有炭素材料の解析＞
（ＣＨＮ分析結果）
ＣＨＮ分析より、炭素原子に対する窒素原子の原子数比（Ｎ／Ｃ）を分析した。結果を表１に示す。
（金属量の分析結果）
結果を表１に示す。
<Analysis of nitrogen-containing carbon materials>
(CHN analysis results)
From CHN analysis, the ratio of the number of nitrogen atoms to carbon atoms (N / C) was analyzed. The results are shown in Table 1.
(Analysis result of metal content)
The results are shown in Table 1.
＜窒素含有炭素材料の粉砕と分級＞
実施例１の粉砕と分級と同様に実施した。
＜電極作製＞
実施例１の電極作製と同様にして作製した。
＜電気化学的測定＞
実施例１の電気化学的測定と同様にして測定した。結果を表１に示す。
<Crushing and classification of nitrogen-containing carbon materials>
It carried out similarly to the grinding | pulverization and classification of Example 1.
<Electrode production>
It was produced in the same manner as the electrode production in Example 1.
<Electrochemical measurement>
The measurement was performed in the same manner as the electrochemical measurement in Example 1. The results are shown in Table 1.
［実施例１１］
＜窒素含有炭素材料の製造＞
実施例５において硝酸コバルト（ＩＩ）・６水和物０．７ｇを１．３ｇに、８００℃の焼成温度を１０００℃に変更した以外は実施例５を反復して２．６ｇの窒素含有炭素材料を得た。
[Example 11]
<Manufacture of nitrogen-containing carbon materials>
Example 5 was repeated except that 0.7 g of cobalt (II) nitrate hexahydrate was changed to 1.3 g and the calcination temperature of 800 ° C. was changed to 1000 ° C. in Example 5. Obtained material.
＜窒素含有炭素材料の解析＞
（ＣＨＮ分析結果）
ＣＨＮ分析より、炭素原子に対する窒素原子の原子数比（Ｎ／Ｃ）を分析した。結果を表１に示す。
（金属量の分析結果）
結果を表１に示す。
<Analysis of nitrogen-containing carbon materials>
(CHN analysis results)
From CHN analysis, the ratio of the number of nitrogen atoms to carbon atoms (N / C) was analyzed. The results are shown in Table 1.
(Analysis result of metal content)
The results are shown in Table 1.
＜窒素含有炭素材料の粉砕と分級＞
実施例１の粉砕と分級と同様に実施した。
＜電極作製＞
実施例１の電極作製と同様にして作製した。
＜電気化学的測定＞
実施例１の電気化学的測定と同様にして測定した。結果を表１に示す。
<Crushing and classification of nitrogen-containing carbon materials>
It carried out similarly to the grinding | pulverization and classification of Example 1.
<Electrode production>
It was produced in the same manner as the electrode production in Example 1.
<Electrochemical measurement>
The measurement was performed in the same manner as the electrochemical measurement in Example 1. The results are shown in Table 1.
［比較例４］
＜窒素含有炭素材料の製造＞
比較例１において８００℃の焼成温度を１０００℃に変更した以外は比較例１を反復して２．８ｇの窒素含有炭素材料を得た。
[Comparative Example 4]
<Manufacture of nitrogen-containing carbon materials>
Comparative Example 1 was repeated except that the firing temperature at 800 ° C. was changed to 1000 ° C. in Comparative Example 1 to obtain 2.8 g of a nitrogen-containing carbon material.
＜窒素含有炭素材料の解析＞
（ＣＨＮ分析結果）
ＣＨＮ分析より、炭素原子に対する窒素原子の原子数比（Ｎ／Ｃ）を分析した。結果を表１に示す。
（金属量の分析結果）
結果を表１に示す。
<Analysis of nitrogen-containing carbon materials>
(CHN analysis results)
From CHN analysis, the ratio of the number of nitrogen atoms to carbon atoms (N / C) was analyzed. The results are shown in Table 1.
(Analysis result of metal content)
The results are shown in Table 1.
＜窒素含有炭素材料の粉砕と分級＞
実施例１の粉砕と分級と同様に実施した。
＜電極作製＞
実施例１の電極作製と同様にして作製した。
＜電気化学的測定＞
実施例１の電気化学的測定と同様にして測定した。結果を表１に示す。
<Crushing and classification of nitrogen-containing carbon materials>
It carried out similarly to the grinding | pulverization and classification of Example 1.
<Electrode production>
It was produced in the same manner as the electrode production in Example 1.
<Electrochemical measurement>
The measurement was performed in the same manner as the electrochemical measurement in Example 1. The results are shown in Table 1.
実施例の窒素含有炭素材料は、高い酸素還元活性を有することがわかる。
実施例７、実施例８、実施例１１、比較例４のＸＲＤを図２に示す。いずれも回折角（２θ）が２４．０〜２６．５°の位置にピークを有し、各ピークの半値幅は、それぞれ２．４°、４．５°、５．９°、８．２°であった。
It turns out that the nitrogen-containing carbon material of an Example has high oxygen reduction activity.
The XRDs of Example 7, Example 8, Example 11, and Comparative Example 4 are shown in FIG. Each has a peak at a diffraction angle (2θ) of 24.0 to 26.5 °, and the half width of each peak is 2.4 °, 4.5 °, 5.9 °, and 8.2, respectively. °.
実施例１、比較例１で得られた窒素含有炭素材料をそれぞれ内径２５ｍｍの石英管に充填し、大気圧下、２００Ｎｃｃ／ ｍｉｎ．の窒素気流中で６０分かけて１０００℃まで昇温し、１０００℃で１時間ホールドして試験用窒素含有炭素材料を得た。 Each of the nitrogen-containing carbon materials obtained in Example 1 and Comparative Example 1 was filled in a quartz tube having an inner diameter of 25 mm, and 200 Ncc / min. In a nitrogen stream, the temperature was raised to 1000 ° C. over 60 minutes, and held at 1000 ° C. for 1 hour to obtain a test nitrogen-containing carbon material.
得られた試験用窒素含有炭素材料の（Ｎ／Ｃ）、ＸＲＤを測定したところ、実施例１の試験用窒素含有炭素材料の（Ｎ／Ｃ）は０．０６、回折角（２θ）が２４．０〜２６．５°の位置にピークを有し、該ピークの半値幅は、２．４°であった。一方、比較例１の試験用窒素含有炭素材料の（Ｎ／Ｃ）は０．０９、回折角（２θ）が２４．０〜２６．５°の位置にピークを有したが、該ピークの半値幅は、８．２°であった。 When the (N / C) and XRD of the obtained nitrogen-containing carbon material for test were measured, (N / C) of the nitrogen-containing carbon material for test of Example 1 was 0.06, and the diffraction angle (2θ) was 24. It had a peak at a position of 0.0 to 26.5 °, and the full width at half maximum of the peak was 2.4 °. On the other hand, (N / C) of the test-containing nitrogen-containing carbon material of Comparative Example 1 had a peak at a position of 0.09 and a diffraction angle (2θ) of 24.0 to 26.5 °. The value range was 8.2 °.
本発明の窒素含有炭素材料は、化学反応の触媒、燃料電池の電極、金属―空気電池の電極等として有用である。
また本実施態様の窒素含有炭素材料の製造方法は、アクリロニトリル等基礎原料の製造において副生物として製造されている青酸の重合体を利用可能であり、工程数が少なく、しかも炭素化収率が高い。そのため、省資源、省エネルギーとなる製造方法として有用である。
The nitrogen-containing carbon material of the present invention is useful as a catalyst for chemical reaction, an electrode for a fuel cell, an electrode for a metal-air cell, and the like.
Further, the method for producing a nitrogen-containing carbon material according to this embodiment can use a polymer of cyanic acid produced as a by-product in the production of basic raw materials such as acrylonitrile, has a small number of steps, and has a high carbonization yield. . Therefore, it is useful as a production method that saves resources and energy.
Claims (4)
ＣｕＫα線をＸ線源として得られるＸ線回折図において、回折角（２θ）が２４．０〜２６．５°の位置にピークを有し、該ピークの半値幅が７．５°以下であって、
Ｆｅ、Ｎｉ、及びＰｔからなる群より選ばれる少なくとも１種の遷移金属を含有する、
窒素含有炭素材料。 A nitrogen-containing carbon material having an atomic ratio (N / C) of nitrogen atoms to carbon atoms of 0.03 to 0.6,
In an X-ray diffraction diagram obtained using CuKα rays as an X-ray source, the diffraction angle (2θ) has a peak at a position of 24.0 to 26.5 °, and the half width of the peak is 7.5 ° or less . And
Containing at least one transition metal selected from the group consisting of Fe, Ni, and Pt,
Nitrogen-containing carbon material.
大気圧下２００Ｎｃｃ／ｍｉｎ．の窒素気流中で６０分かけて１０００℃まで昇温し、１０００℃で１時間保持した後、ＣｕＫα線をＸ線源として得られるＸ線回折図において、回折角（２θ）が２４．０〜２６．５°の位置にピークを有し、該ピークの半値幅が７．５°以下であって、
Ｆｅ、Ｎｉ、及びＰｔからなる群より選ばれる少なくとも１種の遷移金属を含有する、
窒素含有炭素材料。 A nitrogen-containing carbon material having an atomic ratio (N / C) of nitrogen atoms to carbon atoms of 0.03 to 0.6,
200 Ncc / min. Under atmospheric pressure. In an X-ray diffractogram obtained by using CuKα rays as an X-ray source after raising the temperature to 1000 ° C. over 60 minutes in a nitrogen stream and holding at 1000 ° C. for 1 hour, the diffraction angle (2θ) is 24.0. having peaks at 26.5 °, the half-value width of the peak is not more 7.5 ° or less,
Containing at least one transition metal selected from the group consisting of Fe, Ni, and Pt,
Nitrogen-containing carbon material.
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