CN106925317B - A kind of carbon-based catalysis material and its synthetic method - Google Patents
A kind of carbon-based catalysis material and its synthetic method Download PDFInfo
- Publication number
- CN106925317B CN106925317B CN201511028862.6A CN201511028862A CN106925317B CN 106925317 B CN106925317 B CN 106925317B CN 201511028862 A CN201511028862 A CN 201511028862A CN 106925317 B CN106925317 B CN 106925317B
- Authority
- CN
- China
- Prior art keywords
- carbon
- based material
- weight
- peak
- amount
- 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.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 222
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 176
- 239000000463 material Substances 0.000 title claims abstract description 75
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 10
- 238000010189 synthetic method Methods 0.000 title description 2
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 164
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 146
- 239000001301 oxygen Substances 0.000 claims abstract description 100
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 100
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 97
- 239000007787 solid Substances 0.000 claims abstract description 86
- 238000000034 method Methods 0.000 claims abstract description 80
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 77
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 32
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 32
- 239000003513 alkali Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 22
- 150000001336 alkenes Chemical class 0.000 claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims description 39
- 239000002041 carbon nanotube Substances 0.000 claims description 32
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 32
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 23
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 21
- 239000002585 base Substances 0.000 claims description 17
- 239000012298 atmosphere Substances 0.000 claims description 16
- -1 aliphatic cyclic amine Chemical class 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 229910021389 graphene Inorganic materials 0.000 claims description 11
- 229910002804 graphite Inorganic materials 0.000 claims description 11
- 239000010439 graphite Substances 0.000 claims description 11
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 9
- 239000002113 nanodiamond Substances 0.000 claims description 9
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 8
- 239000002134 carbon nanofiber Substances 0.000 claims description 8
- 229910003472 fullerene Inorganic materials 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 8
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 8
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical group C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 8
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 150000001408 amides Chemical class 0.000 claims description 6
- 239000001273 butane Substances 0.000 claims description 6
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 claims description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 150000004982 aromatic amines Chemical class 0.000 claims description 5
- 238000001228 spectrum Methods 0.000 claims description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 4
- CZZZABOKJQXEBO-UHFFFAOYSA-N 2,4-dimethylaniline Chemical compound CC1=CC=C(N)C(C)=C1 CZZZABOKJQXEBO-UHFFFAOYSA-N 0.000 claims description 4
- VOWZNBNDMFLQGM-UHFFFAOYSA-N 2,5-dimethylaniline Chemical compound CC1=CC=C(C)C(N)=C1 VOWZNBNDMFLQGM-UHFFFAOYSA-N 0.000 claims description 4
- MLPVBIWIRCKMJV-UHFFFAOYSA-N 2-ethylaniline Chemical compound CCC1=CC=CC=C1N MLPVBIWIRCKMJV-UHFFFAOYSA-N 0.000 claims description 4
- DOLQYFPDPKPQSS-UHFFFAOYSA-N 3,4-dimethylaniline Chemical compound CC1=CC=C(N)C=C1C DOLQYFPDPKPQSS-UHFFFAOYSA-N 0.000 claims description 4
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 claims description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical group NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 4
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 4
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 4
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical compound CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 claims description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 3
- 229940043237 diethanolamine Drugs 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- KWVPRPSXBZNOHS-UHFFFAOYSA-N 2,4,6-Trimethylaniline Chemical compound CC1=CC(C)=C(N)C(C)=C1 KWVPRPSXBZNOHS-UHFFFAOYSA-N 0.000 claims description 2
- FOYHNROGBXVLLX-UHFFFAOYSA-N 2,6-diethylaniline Chemical compound CCC1=CC=CC(CC)=C1N FOYHNROGBXVLLX-UHFFFAOYSA-N 0.000 claims description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims description 2
- DNSISZSEWVHGLH-UHFFFAOYSA-N butanamide Chemical compound CCCC(N)=O DNSISZSEWVHGLH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- ZMCUDHNSHCRDBT-UHFFFAOYSA-M caesium bicarbonate Chemical compound [Cs+].OC([O-])=O ZMCUDHNSHCRDBT-UHFFFAOYSA-M 0.000 claims description 2
- 229910000025 caesium bicarbonate Inorganic materials 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000003983 crown ethers Chemical class 0.000 claims description 2
- 229940113088 dimethylacetamide Drugs 0.000 claims description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 2
- KEDRKJFXBSLXSI-UHFFFAOYSA-M hydron;rubidium(1+);carbonate Chemical compound [Rb+].OC([O-])=O KEDRKJFXBSLXSI-UHFFFAOYSA-M 0.000 claims description 2
- 229940047889 isobutyramide Drugs 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- VSHTWPWTCXQLQN-UHFFFAOYSA-N n-butylaniline Chemical compound CCCCNC1=CC=CC=C1 VSHTWPWTCXQLQN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002071 nanotube Substances 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 claims description 2
- 229940080818 propionamide Drugs 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 claims description 2
- 229910001866 strontium hydroxide Inorganic materials 0.000 claims description 2
- MKARNSWMMBGSHX-UHFFFAOYSA-N 3,5-dimethylaniline Chemical compound CC1=CC(C)=CC(N)=C1 MKARNSWMMBGSHX-UHFFFAOYSA-N 0.000 claims 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 claims 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitrogen oxide Substances O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 1
- 125000002252 acyl group Chemical group 0.000 claims 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 229940045713 antineoplastic alkylating drug ethylene imines Drugs 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 claims 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 claims 1
- 229960003753 nitric oxide Drugs 0.000 claims 1
- 239000001294 propane Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 23
- 238000001035 drying Methods 0.000 abstract description 18
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 16
- 238000004458 analytical method Methods 0.000 description 15
- 125000004430 oxygen atom Chemical group O* 0.000 description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000001914 filtration Methods 0.000 description 12
- 125000004429 atom Chemical group 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 10
- 125000004433 nitrogen atom Chemical group N* 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000000908 ammonium hydroxide Substances 0.000 description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000002048 multi walled nanotube Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000006356 dehydrogenation reaction Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000004611 spectroscopical analysis Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000005864 Sulphur Chemical group 0.000 description 4
- 230000003001 depressive effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 125000004437 phosphorous atom Chemical group 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 2
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- 229910002703 Al K Inorganic materials 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical class NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- UCVMQZHZWWEPRC-UHFFFAOYSA-L barium(2+);hydrogen carbonate Chemical compound [Ba+2].OC([O-])=O.OC([O-])=O UCVMQZHZWWEPRC-UHFFFAOYSA-L 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- CVDTXIRZVNJRRD-UHFFFAOYSA-N carbonic acid;rubidium Chemical compound [Rb].OC(O)=O CVDTXIRZVNJRRD-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229920006248 expandable polystyrene Polymers 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 description 1
- 239000002370 magnesium bicarbonate Substances 0.000 description 1
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 description 1
- 235000014824 magnesium bicarbonate Nutrition 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910001952 rubidium oxide Inorganic materials 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- WJMMDJOFTZAHHS-UHFFFAOYSA-L strontium;carbonic acid;carbonate Chemical compound [Sr+2].OC([O-])=O.OC([O-])=O WJMMDJOFTZAHHS-UHFFFAOYSA-L 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
- C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/24—Nitrogen compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of carbon-based materials, and on the basis of the total weight of the carbon-based material, which contains the metallic element of the carbon of 60-99 weight %, the nitrogen of 0.1-16 weight %, the oxygen element of 0.5-20 weight % and 0.05-8 weight %.The present invention also provides a kind of methods for preparing above-mentioned carbon-based material, and this method comprises the following steps: (1) mixing solid carbon source, presoma and water, obtain mixed material；Wherein, the presoma contains organic alkali source and inorganic alkali source；(2) mixed material is subjected to hydro-thermal process, the material after obtaining hydro-thermal process；And the solid in the material after hydro-thermal process is separated and is dried, the material after being dried；(3) material after drying is roasted.The present invention also provides purposes of the carbon-based material as described above in catalysis oxidation reactions of hydrocarbons.The present invention can improve the selectivity and conversion ratio that hydrocarbon oxidation prepares alkene simultaneously.
Description
Technical field
The present invention relates to technical field of material chemistry, and in particular, to a kind of carbon-based material, a kind of method for preparing carbon-based material
With the purposes of the carbon-based material.
Background technique
Carbon-based material includes carbon nanotube, graphene, fullerene, carbon nano-fiber and Nano diamond etc..Carbon substrate
Material can be used as the catalysis material of oxidizing hydrocarbons especially alkane, such as: there are document (Applied Catalysis, 29 (1987)
311-326) reporting becomes styrene for oxidative dehydrogenation of ethylbenzene for catalyst using active carbon, and there are also document (ACTA
PHYSICA POLONIC A, 118 (2010) 459-464) to report using active carbon be that normal butane is converted butylene by catalyst
And butadiene.
Studies have shown that miscellaneous if modifying oxygen-containing, nitrogen etc. on nano-carbon material (such as carbon nanotubes and graphene) surface
The saturation of atom and unsaturation functional group, thus it is possible to vary the catalytic activity of nano-carbon material, it such as can be by nano-carbon material
It carries out oxidation processes realization and introduces oxygen atom in nano-carbon material, to increase containing for oxygen-containing functional group in nano-carbon material
Amount.For example, can be by nano-carbon material in strong acid (such as HNO3、H2SO4) and/or strong oxidizing solution (such as H2O2、KMnO4) in into
Row back flow reaction can also assist carrying out microwave heating or sonic oscillation while back flow reaction, to enhance oxidation reaction
Effect.
It may skeleton knot to nano-carbon material but carry out back flow reaction in strong acid and/or strong oxidizing solution
Structure has an adverse effect, or even destroys the skeleton structure of nano-carbon material.Such as: nano-carbon material is aoxidized with nitric acid,
Although a large amount of oxygen-containing functional groups can be introduced on nano-carbon material surface, easily cause nano-carbon material be cut off and/or
The defects of graphite network structure position is obviously increased, so as to reduce the performance of nano-carbon material, such as thermal stability.In addition,
By carrying out back flow reaction in strong acid and/or strong oxidizing solution, when introducing oxygen atom, the introduction volume of oxygen atom is to reaction
The dependence of operating condition is high, and fluctuation range is wider, is not easy accurately to control.
Alkene especially alkadienes and aromatic olefin are important industrial chemicals, such as butadiene is production synthetic rubber
The primary raw material of (such as butadiene-styrene rubber, butadiene rubber, nitrile rubber, neoprene).It is raw using styrene and butadiene copolymer
It produces the extensive resin of various uses (such as ABS resin, SBS resin, BS resin and MBS resin), makes butadiene in production of resins
Gradually occupy an important position.In addition, butadiene can also be used to produce ethylidene norbornene (EP rubbers Third monomer), Isosorbide-5-Nitrae-fourth
Glycol, adiponitrile (nylon66 fiber monomer), sulfolane, anthraquinone and tetrahydrofuran etc., therefore butadiene is also important basic chemical industry
Raw material.In addition, styrene is also important the monomer of synthetic rubber and plastics, can be used to produce butadiene-styrene rubber, polystyrene
With foamed polystyrene etc.；It is also used for being copolymerized the engineering plastics for manufacturing a variety of different purposes from other monomers.Such as with acrylonitrile, fourth
Diene, which is copolymerized, is made ABS resin, is widely used in various household electrical appliance and industrial；It is with SAN resin made from acrylonitrile compolymer
Impact resistance, bright in color resin；It is a kind of thermoplastic elastomer with SBS obtained by butadiene copolymer, is widely used as polychlorostyrene second
Alkene, polyacrylic modifying agent etc..Styrene is handed over mainly for the production of styrene series resin and butadiene-styrene rubber, and production ion
Change one of the raw material of resin and pharmaceuticals.In addition, styrene can also be used in the industries such as pharmacy, dyestuff, pesticide and ore dressing.
Hydrocarbon oxidative dehydrogenation is to prepare the important method of alkene, such as butane oxidation dehydrogenation can be generated 1- butylene, 1- fourth
Alkene oxidative dehydrogenation can generate 1,3- butadiene in turn；Vinylbenzene oxidative dehydrogenation can also be generated into styrene.But hydrocarbon oxidation is de-
When hydrogen prepares alkene, the problem of improving simultaneously is difficult in the prevalence of selectivity and conversion ratio.
Summary of the invention
The purpose of the present invention is in the presence of overcoming hydrocarbon oxidative dehydrogenation to prepare alkene selectivity and conversion ratio be generally difficult to
The problem of improving simultaneously, provide it is a kind of can catalytic hydrocarbon oxidative dehydrogenation prepare alkene and obtain simultaneously highly selective and conversion ratio
The purposes of carbon-based material, the preparation method of the carbon-based material and the carbon-based material.
It was found by the inventors of the present invention that carrying out water to carbon source material using the presoma containing organic alkali source and inorganic alkali source
Heat treatment is capable of forming to aoxidize with catalytic hydrocarbon and make by the solid separation in the material after hydro-thermal process and after drying and roasting
The activity of standby alkene simultaneously obtains highly selective and conversion ratio carbon-based material simultaneously, results in the present invention.
On the one hand, the present invention provides a kind of carbon-based materials, on the basis of the total weight of the carbon-based material, the carbon-based material
Carbon containing 60-99 weight %, the nitrogen of 0.1-16 weight %, the oxygen element of 0.5-20 weight % and 0.05-8 weight
Measure the metallic element of %；Wherein, the metallic element includes at least one of alkali metal element and/or alkali earth metal,
In the x-ray photoelectron spectroscopy of the carbon-based material, the amount and 531.8- of the oxygen element that the peak within the scope of 533.1-533.5eV determines
The ratio of the amount for the oxygen element that peak within the scope of 532.2eV determines is in the range of 1-10.
On the other hand, the present invention also provides a kind of method for preparing carbon-based material, this method comprises the following steps: (1)
Solid carbon source, presoma and water are mixed, mixed material is obtained；Wherein, the presoma contains organic alkali source and inorganic
Alkali source, organic alkali source include machine amine and/or quaternary ammonium base；The inorganic alkali source include metallic element hydroxide and/
Or the salt of the metallic element in alkalinity；The metallic element includes at least one in alkali metal element and/or alkali earth metal
Kind；(2) the mixed material for obtaining step (1) carries out hydro-thermal process, the material after obtaining hydro-thermal process；And separate water
The solid in material after heat treatment；(3) solid in the material after hydro-thermal process that step (2) obtains is roasted.
On the other hand, the present invention also provides the carbon-based materials that method as described above is prepared.
In another aspect, the present invention also provides the carbon that carbon-based material as described above and method as described above are prepared
Purposes of the sill in catalysis oxidation reactions of hydrocarbons.
Through the above technical solutions, the present invention can improve the selectivity and conversion ratio that hydrocarbon oxidation prepares alkene simultaneously.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of carbon-based materials, and on the basis of the total weight of the carbon-based material, which contains 60-
The carbon of 99 weight %, the nitrogen of 0.1-16 weight %, the oxygen element of 0.5-20 weight % and 0.05-8 weight % gold
Belong to element, the metallic element includes at least one of alkali metal element and/or alkali earth metal；Wherein, the carbon substrate
In the x-ray photoelectron spectroscopy of material, the amount and 531.8-532.2eV of the oxygen element that the peak within the scope of 533.1-533.5eV determines
The ratio of the amount for the oxygen element that peak in range determines is in the range of 1-10.
Wherein it is preferred to which the peak within the scope of 533.1-533.5eV determines in the x-ray photoelectron spectroscopy of the carbon-based material
Oxygen element amount and 531.8-532.2eV within the scope of peak determine oxygen element amount ratio in the range of 1.2-5.Into
One step preferably, in the x-ray photoelectron spectroscopy of the carbon-based material, oxygen element that peak within the scope of 533.1-533.5eV determines
Amount and 531.8-532.2eV within the scope of peak determine oxygen element amount ratio in the range of 1.5-2.5.By X-ray
The area of O1s spectral peak in photoelectron spectroscopy can determine the total amount of O element in carbon-based material.Wherein, 533.1-533.5eV model
The amount for the oxygen element that peak in enclosing determines can indicate the Relative mole content of C-O group, the peak within the scope of 531.8-532.2eV
The amount of determining oxygen element can indicate the Relative mole content of C=O group.
In the present invention, in carbon-based material the content of each element be by carbon-based material 300 DEG C at a temperature of in helium atmosphere
After middle drying 3 hours, the numerical value measured using X-ray photoelectron spectroscopy, measuring method for known to those skilled in the art,
It does not repeat herein.
In the present invention, x-ray photoelectron spectroscopy map refers to that XPS map, XPS map can be normal according to instrument analysis field
The method of rule measures to obtain, and the calculating of the amount for the element that peak in x-ray photoelectron spectroscopy in particular range determines can be according to
The method of instrument analysis field routine is calculated, such as can be measured according to the specification of x-ray photoelectron spectroscopy
And quantitative calculating is carried out using the data software that x-ray photoelectron spectroscopy carries, the present invention does not have particular/special requirement to this.The carbon
The x-ray photoelectron spectroscopy data of sill be sample 300 DEG C at a temperature of handle 3h in helium atmosphere after measure.
Wherein, when the content value of measurement is lower than 0.1 weight %, the content of the element is denoted as 0.
In the present invention, from the point of view of the catalytic capability for further increasing the carbon-based material, it is preferable that carbon-based with this
On the basis of the total weight of material, which contains the carbon of 80-98 weight %, the nitrogen of 0.2-8 weight %, 1-10
The oxygen element of weight % and the metallic element of 0.1-4 weight %.It is highly preferred that the carbon-based material contains the carbon of 85-95 weight %
Element, the nitrogen of 0.5-6 weight %, the oxygen element of 3-8 weight % and 0.2-3 weight % metallic element.
In the present invention, it is preferable that the peak in the x-ray photoelectron spectroscopy of the carbon-based material, within the scope of 529.5-530.8eV
The amount of determining oxygen element accounts for model of the ratio in 0.01-0.1 of the amount for the oxygen element that the peak within the scope of 526.0-535.0eV determines
In enclosing, more preferably in the range of 0.03-0.08.Wherein, the amount base for the oxygen element that the peak within the scope of 529.5-530.8eV determines
Originally the Relative mole content of oxygen contained by metal-oxygen key group in carbon-based material can be indicated, within the scope of 526.0-535.0eV
The amount for the oxygen element that peak determines can indicate the Relative mole content of oxygen contained by all oxygen-containing groups of carbon-based material substantially.
Carbon-based material according to the present invention, in the x-ray photoelectron spectroscopy of the carbon-based material, 398.0-400.5eV range
The ratio of the amount for the nitrogen that the amount for the nitrogen that interior peak determines and the peak within the scope of 395.0-405.0eV determine is in 0.5-
In the range of 0.85；More preferably in the range of 0.6-0.75.It can be with by the area of the N1s spectral peak in x-ray photoelectron spectroscopy
Determine the total amount of nitrogen in carbon-based material, generally, the amount for the nitrogen that the peak within the scope of 395.0-405.0eV determines is basic
It can indicate the Relative mole content of nitrogen contained by whole nitrogen-containing groups in carbon-based material.Wherein, within the scope of 398.0-400.5eV
The amount of nitrogen that determines of peak can indicate (such as pyrroles, pyridine, amide and the table of nitrogen contained by NH group in carbon-based material substantially
Nitrogen in the amino of face) Relative mole content.
Carbon-based material according to the present invention, in the x-ray photoelectron spectroscopy of the carbon-based material, 400.6-401.5eV range
The ratio of the amount for the nitrogen that the amount for the nitrogen that interior peak determines and the peak within the scope of 395.0-405.0eV determine is in 0.15-
In the range of 0.5；More preferably in the range of 0.25-0.4.Wherein, the nitrogen that the peak within the scope of 400.6-401.5eV determines
Amount can indicate the Relative mole content of contained graphite mould nitrogen in carbon-based material, the peak within the scope of 395.0-405.0eV substantially
The amount of determining nitrogen can indicate the Relative mole content of nitrogen contained by whole nitrogen-containing groups of carbon-based material substantially.
Carbon-based material according to the present invention, in the x-ray photoelectron spectroscopy of the carbon-based material, 283.8-284.2eV range
The ratio of the amount for the carbon that the amount for the carbon that interior peak determines and the peak within the scope of 280.0-294.0eV determine is in 0.6-1
In the range of；More preferably in the range of 0.7-0.9.Wherein, the amount for the carbon that the peak within the scope of 283.8-284.2eV determines
Substantially the Relative mole content of contained graphite mould carbon in carbon-based material can be indicated, the peak within the scope of 280.0-294.0eV determines
The amount of carbon can indicate the Relative mole content of carbon contained by whole carbon-containing groups of carbon-based material substantially.
Carbon-based material according to the present invention, in the x-ray photoelectron spectroscopy of the carbon-based material, 286.2-286.6eV range
The sum of amount of carbon that the amount for the carbon that interior peak determines and the peak within the scope of 288.6-289.0eV determine and 280.0-
The ratio of the amount for the carbon that peak within the scope of 294.0eV determines is in the range of 0.02-0.2；More preferably 0.05-0.15's
In range.The total amount of C element in carbon-based material can be determined by the area of the C1s spectral peak in x-ray photoelectron spectroscopy, generally
The amount on ground, the carbon that the peak within the scope of 280.0-294.0eV determines can indicate whole carbon-containing groups of carbon-based material substantially
The Relative mole content of contained carbon.Wherein, the amount for the carbon that the peak within the scope of 286.2-286.6eV determines can refer to substantially
Show the Relative mole content of carbon contained by C-O group in carbon-based material (carbon in such as carboxyl, acid anhydride and ester), 288.6-289.0eV
The amount for the carbon that peak in range determines can indicate that carbon contained by C=O group is (in such as hydroxyl and ether in carbon-based material substantially
Carbon) Relative mole content.
Carbon-based material according to the present invention, in the x-ray photoelectron spectroscopy of the carbon-based material, 286.2-286.6eV range
The ratio of the amount for the carbon that the amount for the carbon that interior peak determines and the peak within the scope of 288.6-289.0eV determine is in 0.3-2
In the range of；More preferably in the range of 0.6-1.7.
In the present invention, position combination as corresponding to the summit at the peak at above-mentioned each peak be can determine that, by mentioned earlier range
Determining peak refer to combination corresponding to summit can peak within that range, in the range may include a peak, can also
To include more than two peaks.Such as: the peak within the scope of 280.0-294.0eV refers to that combination corresponding to summit can be in
Whole peaks in the range of 280.0-294.0eV.
Carbon-based material according to the present invention, wherein the W of the carbon-based material500/W800It can be in the range of 0.02-0.5
It is interior；The W of the preferably described carbon-based material500/W800In the range of 0.05-0.25.Under the preferable case, the carbon-based material
Better catalytic effect can be obtained when being used as catalyst, when being especially used as the catalyst of hydrocarbons dehydrogenation reaction, energy
Obtain higher feed stock conversion and selectivity of product.Wherein, W800Refer to air atmosphere and 25 DEG C of initial temperature and 10
DEG C/Elevated Temperature Conditions of min under, slip of the carbon-based material in the weight at 800 DEG C relative to the weight at 400 DEG C, i.e.,
(carbon-based material is in the weight and weight difference of the carbon-based material at 800 DEG C at 400 DEG C)/carbon-based material exists
Weight at 400 DEG C, W500Under the Elevated Temperature Conditions for referring to air atmosphere and 25 DEG C of initial temperature and 10 DEG C/min, the carbon
Slip of the sill in the weight at 500 DEG C relative to the weight at 400 DEG C, i.e. (weight of the carbon-based material at 400 DEG C
Amount is with the carbon-based material in the weight difference at 500 DEG C) the weight of/carbon-based material at 400 DEG C.
Carbon-based material according to the present invention, it is preferable that the distribution of nitrogen therein and oxygen element and metallic element compared with
Uniformly.Such as when being analyzed by X-ray microregion element, in the identical different X-ray microcells of the area on the surface of the carbon-based material, nitrogen member
The coefficient of variation of the content of element and oxygen element and metallic element is 20% hereinafter, more preferably 15% hereinafter, particularly preferably existing
10% hereinafter, particularly preferably below 5%.Wherein, X-ray microcell refers to selected when carrying out the analysis of X-ray microregion element
Observation area.Wherein, the concept of the coefficient of variation refers to the standard deviation of multiple measured values and the percentage of their average, that is, becomes
Different coefficient CV=(standard deviation SD/ average value MN) × 100%.Wherein, the method for carrying out the analysis of X-ray microregion element can be according to instrument
The method of device analysis field routine measures to obtain, such as specific test method may include: along length with energy depressive spectroscopy in 25-
The length direction of carbon-based material such as carbon nanotube in the range of 250nm is scanned, and determines nitrogen-atoms and oxygen atom respectively
And concentration or content (measurement 5 concentration or content) of the metallic atom on the length direction, by same nano-carbon material system
It is scanned Electronic Speculum-energy spectrum analysis respectively at five effective samples, each sample takes 5 different carbon nanotubes to be scanned, nitrogen
Atom and oxygen atom and metallic atom respectively obtain 25 concentration or content data, calculate corresponding nitrogen-atoms and oxygen atom and
The coefficient of variation of metallic atom.The coefficient of variation refers to the standard deviation of 25 measured values and the percentage of their average herein,
That is coefficient of variation CV=(standard deviation SD/ average value MN) × 100%.In order to preferably reflect the nitrogen in carbon-based material and
The distributing homogeneity of oxygen element and metallic element, the area on the surface of selected carbon-based material in the analysis of X-ray microregion element
It can be 10-250nm2, preferably 20-200nm2。
Wherein, the structural form of the carbon-based material may include carbon nanotube, graphene, fullerene, nano carbon particle,
At least one of active carbon, thin layer graphite, carbon nano-fiber and structural form of Nano diamond.
Wherein, the carbon-based material can for carbon nanotube, graphene, fullerene, nano carbon particle, active carbon,
One of carbon-based material of thin layer graphite, carbon nano-fiber and nano diamond structure or a variety of mixtures.Wherein, described
Carbon-based material, which has, is selected from carbon nanotube, graphene, fullerene, nano carbon particle, active carbon, thin layer graphite, carbon nano-fiber
With the structure of Nano diamond.
Wherein it is preferred to which the metallic element includes at least one of lithium, sodium, potassium, rubidium, caesium, magnesium, calcium, strontium and barium.
The present invention also provides a kind of methods for preparing carbon-based material, and this method comprises the following steps: (1) by solid carbon
Source, presoma and water mixing, obtain mixed material；Wherein, the presoma contains organic alkali source and inorganic alkali source, described
Organic alkali source includes machine amine and/or quaternary ammonium base；The inorganic alkali source include metallic element hydroxide and/or in alkalinity
The salt of metallic element；The metallic element includes at least one of alkali metal element and/or alkali earth metal；It (2) will step
Suddenly the mixed material that (1) obtains carries out hydro-thermal process, the material after obtaining hydro-thermal process；And after separating hydro-thermal process
Solid in material；(3) solid in the material after hydro-thermal process that step (2) obtains is roasted.
According to the method for the present invention, wherein the mixed time and temperature does not have particular/special requirement, can become in a big way
Change, such as the mixed time can be 0.5-72h, mixed temperature can be 20-80 DEG C.
According to the method for the present invention, wherein the nitrogen in carbon and organic alkali source in the solid carbon source
Molar ratio can be 1:(0.002-50), preferably 1:(0.005-20), more preferably 1:(0.01-10).
According to the method for the present invention, wherein the molar ratio of carbon and the inorganic alkali source in the solid carbon source can
Think 1:(0.005-10), preferably 1:(0.008-5), more preferably 1:(0.01-2).
According to the method for the present invention, wherein the weight ratio of carbon and water in the solid carbon source can be 1:(1-
100), preferably 1:(5-20).
According to the method for the present invention, particularly preferably, the presoma also contains hydrogen peroxide, in organic alkali source
Nitrogen and the molar ratio of hydrogen peroxide are 1:(0.01-10)；It is highly preferred that nitrogen and peroxidating in organic alkali source
The molar ratio of hydrogen is 1:(0.05-5).
According to the method for the present invention, wherein hydro-thermal process refers at 100 DEG C or more under air-proof condition at autogenous pressures
Holding part water maintains the reaction condition of liquid, and hydro-thermal process can heat water so that part water nature gas under air-proof condition
Change pressurization to obtain；Preferably, the temperature for carrying out hydro-thermal process is 105-200 DEG C；More preferably 120-180 DEG C.Wherein, at hydro-thermal
The time of reason can be 0.5-96h, preferably 2-72h.
Wherein, the operation of the solid in material after separating hydro-thermal process can be by being centrifuged and/or filtering etc. conventional point
It is carried out from mode.
Wherein, after the solid in material after separating hydro-thermal process, solid can be dried, condition is dried
It can change in a big way, the condition of the drying is not particularly limited in the present invention, can be conventional selection, preferably
Ground, the temperature being dried are 80-180 DEG C, time 0.5-24h.The drying can carry out under normal pressure, can also subtract
It is carried out under pressure (i.e. negative pressure).
Wherein, the roasting can carry out in inert atmosphere, can also carry out in oxygen-containing atmosphere, can also be successively
It is carried out in inert atmosphere and oxygen-containing atmosphere, wherein the inert atmosphere refers to the atmosphere formed by non-active gas, institute
State non-active gas such as group 0 element gas (such as argon gas) and/or nitrogen.Preferably, the roasting is in the gas containing oxygen
Middle progress, on the basis of the total volume of the gas containing oxygen, the content of the oxygen in the gas containing oxygen is 2-25 volume %.
In order to more convenient and implement the present invention at low cost, under preferable case, the roasting can carry out in air.
Wherein, the condition roasted can change in a big way, such as the temperature of roasting is 200-500 DEG C, excellent
It is selected as 300-450 DEG C, the time of roasting is 0.5-48h, preferably 2-24h.The strategy of temperature programming can be used by carrying out roasting
Heated, for example, roasting temperature be 200-450 DEG C when, 1-12h is roasted at 200-300 DEG C first, is then existed
1-12h is roasted at 310-450 DEG C；Such as the temperature of roasting be 300-450 DEG C when, roast 1-12h at 300-350 DEG C first,
Then 1-12h is roasted at 380-450 DEG C.Wherein, room temperature can be cooled to natural cooling after roasting.
According to the method for the present invention, wherein selecting for the solid carbon source can be the selection of carbon catalytic field routine, only
The catalysis aoxidized after the solid carbon source hydrothermal treatment with catalytic hydrocarbon, such as the solid carbon source is wanted to can wrap
Include carbon nanotube, graphene, fullerene, nano carbon particle, active carbon, thin layer graphite, carbon nano-fiber and Nano diamond etc.
At least one of.Preferably, the solid carbon source includes at least one of carbon nanotube, Nano diamond and graphene.
Wherein, the carbon nanotube may include single-walled carbon nanotube and/or multi-walled carbon nanotube.The carbon nanotube
Specific surface area can change in a big way, for example, 20-1000m2/ g, preferably 30-500m2/g.The carbon nanotube can
It can also be prepared according to literature method with being commercially available, this is does not repeat known to those skilled in the art herein.
In the case of with the method for the invention it is preferred to, when the solid carbon source is multi-walled carbon nanotube, the multi wall carbon
The W of nanotube500/W800It can be in the range of 0.02-0.5；The W of the more preferably described multi-walled carbon nanotube500/W800?
In the range of 0.05-0.25.Under the preferable case, the carbon-based material that method of the invention obtains can when being used as catalyst
Better catalytic effect is obtained, when being especially used as the catalyst of hydrocarbons dehydrogenation reaction, higher raw material conversion can be obtained
Rate and selectivity of product.Wherein, W800Under the Elevated Temperature Conditions for referring to air atmosphere and 25 DEG C of initial temperature and 10 DEG C/min,
Slip of the solid carbon source in the weight at 800 DEG C relative to the weight at 400 DEG C, i.e., (solid carbon source is at 400 DEG C
Under weight and the solid carbon source in the weight difference at 800 DEG C) the weight of/solid carbon source at 400 DEG C, W500Refer to
Under the Elevated Temperature Conditions of air atmosphere and 25 DEG C of initial temperature and 10 DEG C/min, weight of the solid carbon source at 500 DEG C
Relative to the slip of the weight at 400 DEG C, i.e., (weight of the solid carbon source at 400 DEG C and the solid carbon source are 500
Weight difference at DEG C) the weight of/solid carbon source at 400 DEG C.
In a kind of more preferably embodiment of the invention, the solid carbon source is multi-walled carbon nanotube, described more
The specific surface area of wall carbon nano tube is 50-500m2/ g, preferably 100-400m2/g；The W of the multi-walled carbon nanotube500/W800It can
In the range of 0.02-0.5；The W of the more preferably described multi-walled carbon nanotube500/W800In the range of 0.05-0.25.
Wherein, the solid carbon source can also contain oxygen element, nitrogen and remaining nonmetalloid according to source difference
(such as phosphorus atoms and sulphur atom), can also be without containing oxygen element, nitrogen and remaining nonmetalloid (such as phosphorus atoms and sulphur original
Son).
According to the method for the present invention, when the solid carbon source contains oxygen element, wherein the content of oxygen element is generally not high
In 2 weight %, preferably not higher than 0.5 weight %, it is further preferably not higher than 0.2 weight %.
According to the method for the present invention, when the solid carbon source contains nitrogen, wherein the content of nitrogen is generally not high
In 0.5 weight %, preferably not higher than 0.2 weight %, it is further preferably not higher than 0.1 weight %.
According to the method for the present invention, when the solid carbon source contains remaining nonmetalloid (such as phosphorus atoms and sulphur atom),
Wherein in the solid carbon source oxygen atom and remaining nonmetallic heteroatoms (such as phosphorus atoms and sulphur atom) outside nitrogen-atoms it is total
(based on the element) is measured generally not higher than 0.5 weight %, preferably not higher than 0.2 weight %, is further preferably not higher than 0.1
Weight %.
According to the method for the present invention, the organic amine may include aliphatic amine, hydramine, amide, aliphatic cyclic amine and aromatic amine
One of or it is a variety of.
In the present invention, the quaternary ammonium base can be various organic level Four ammonium alkali；The aliphatic amine can be NH3In extremely
The various compounds that few hydrogen is formed after being replaced by aliphatic alkyl (preferably alkyl)；The hydramine can be NH3In
The various compounds that at least one hydrogen is formed after being replaced by the aliphatic alkyl (preferably alkyl) of hydroxyl；The amide can be with
The compound formed after being replaced for the hydroxyl in carboxylic acid by amino (or amido)；The aliphatic cyclic amine can be NH3In at least one
The various compounds that a hydrogen is formed after being replaced by cycloalkyl group；The aromatic amine can be NH3In at least one hydrogen it is fragrant
The various compounds that alkyl is formed after replacing.
Specifically, the quaternary ammonium base can be quaternary ammonium base shown in formula I, what the aliphatic amine can indicate for Formula II
Aliphatic amine, the hydramine can be the hydramine such as formula III expression:
(Formulas I)
In Formulas I, R1、R2、R3And R4Respectively C1-C4Alkyl, C1-C4Alkyl include C1-C4Straight chained alkyl and C3-C4
Branched alkyl, such as: R1、R2、R3And R4It can be respectively methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, different
Butyl or tert-butyl.
R5(NH2)n(Formula II)
In Formula II, n is an integer of 1 or 2.When n is 1, R5For C1-C6Alkyl, including C1-C6Straight chained alkyl and C3-C6
Branched alkyl, such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, n-pentyl, new penta
Base, isopentyl, tertiary pentyl or n-hexyl.When n is 2, R5For C1-C6Alkylidene, including C1-C6Straight-chain alkyl-sub and C3-C6
Branched alkylidene, such as methylene, ethylidene, sub- n-propyl, sub- normal-butyl, sub- n-pentyl or sub- n-hexyl.More preferably fat
Race's amine compounds are one of ethamine, n-butylamine, butanediamine and hexamethylene diamine or a variety of.
(HOR6)mNH(3-m)(formula III)
In formula III, m R6It is identical or different, respectively C1-C4Alkylidene, including C1-C4Straight-chain alkyl-sub and C3-
C4Branched alkylidene, such as methylene, ethylidene, sub- n-propyl and sub- normal-butyl；M is 1,2 or 3.It is highly preferred that the hydramine
Compound is one of monoethanolamine, diethanol amine and triethanolamine or a variety of.
Wherein, the specific example of the aliphatic amine can include but is not limited to ethamine, n-propylamine, n-butylamine, two positive third
At least one of amine, butanediamine and hexamethylene diamine.The specific example of the fatty alcohol amine can include but is not limited to monoethanolamine,
At least one of diethanol amine and triethanolamine；The specific example of the quaternary ammonium base can include but is not limited to tetramethyl hydrogen-oxygen
Change at least one of ammonium, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide.The amide it is specific
Example can include but is not limited to formamide, acetamide, propionamide, butyramide, isobutyramide, acrylamide, polyacrylamide,
At least one of caprolactam, dimethylformamide and dimethyl acetamide.The specific example of the aliphatic cyclic amine may include
But it is not limited to triethylenediamine, diethylenetriamines, hexa, hexamethylene imine, triethylenediamine, ring second
At least one of alkene imines, morpholine, piperazine and cyclohexylamine.The specific example of the aromatic amine can include but is not limited to benzene
Amine, diphenylamines, benzidine, o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine, o-toluidine, m-toluidine, open-chain crown ether,
23 dimethyl aniline, 2,4- dimethylaniline, 2,5- dimethylaniline, 2,6- dimethylaniline, 3,4- dimethylaniline, 3,
At least one in 5- dimethylaniline, 2,4,6- trimethylaniline, o ethyl aniline, N- butylaniline and 2,6- diethylaniline
Kind.
Wherein, the example of the inorganic alkali source can include but is not limited to lithium hydroxide, sodium hydroxide, potassium hydroxide, hydrogen
Rubidium oxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, carbonic acid
Rubidium, cesium carbonate, calcium bicarbonate, calcium carbonate, magnesium bicarbonate, magnesium carbonate, strontium bicarbonate, strontium carbonate, barium bicarbonate, barium carbonate, carbon
At least one of sour hydrogen lithium, sodium bicarbonate, saleratus, rubidium bicarbonate and caesium bicarbonate.
On the other hand, the present invention also provides the carbon-based materials that method as described above is prepared.
Wherein, the carbon-based material that this method obtains can the carbon containing 60-99 weight %, 0.1-16 weight % nitrogen
The metallic element of element, the oxygen of 0.5-20 weight % and 0.05-8 weight %, preferably comprise 80-98 weight % carbon,
The metallic element of the nitrogen of 0.2-8 weight %, the oxygen element of 1-10 weight % and 0.1-4 weight %, further preferably 85-95
The carbon of weight %, the nitrogen of 0.5-6 weight %, the oxygen element of 3-8 weight % and 0.2-3 weight % metallic element.
Wherein, in the x-ray photoelectron spectroscopy for the carbon-based material that this method obtains, the peak within the scope of 533.1-533.5eV
Range of the ratio of the amount for the oxygen element that the amount of determining oxygen element and the peak within the scope of 531.8-532.2eV determine in 1-10
It is interior.
Wherein, in the x-ray photoelectron spectroscopy for the carbon-based material that this method obtains, the peak within the scope of 529.5-530.8eV
The amount of determining oxygen element accounts for model of the ratio in 0.01-0.1 of the amount for the oxygen element that the peak within the scope of 526.0-535.0eV determines
In enclosing.
Wherein, in the x-ray photoelectron spectroscopy for the carbon-based material that this method obtains, the peak within the scope of 398.0-400.5eV
Model of the ratio of the amount for the nitrogen that the amount of determining nitrogen and the peak within the scope of 395.0-405.0eV determine in 0.5-0.85
In enclosing.
Wherein, in the x-ray photoelectron spectroscopy for the carbon-based material that this method obtains, the peak within the scope of 400.6-401.5eV
Model of the ratio of the amount for the nitrogen that the amount of determining nitrogen and the peak within the scope of 395.0-405.0eV determine in 0.15-0.5
In enclosing.
Wherein, in the x-ray photoelectron spectroscopy for the carbon-based material that this method obtains, the peak within the scope of 283.8-284.2eV
Range of the ratio of the amount for the carbon that the amount of determining carbon and the peak within the scope of 280.0-294.0eV determine in 0.6-1
It is interior.
Wherein, in the x-ray photoelectron spectroscopy for the carbon-based material that this method obtains, the peak within the scope of 286.2-286.6eV
The sum of amount of carbon that the amount of determining carbon and the peak within the scope of 288.6-289.0eV determine and 280.0-294.0eV
The ratio of the amount for the carbon that peak in range determines is in the range of 0.02-0.2.
Wherein, in the x-ray photoelectron spectroscopy for the carbon-based material that this method obtains, the peak within the scope of 286.2-286.6eV
Range of the ratio of the amount for the carbon that the amount of determining carbon and the peak within the scope of 288.6-289.0eV determine in 0.3-2
It is interior.
The carbon-based material obtained according to the method for the present invention, W500/W800It is preferred that more preferably existing in the range of 0.02-0.5
In the range of 0.05-0.25.Better catalytic effect can be obtained in this way, be especially used as the catalysis of hydrocarbons dehydrogenation reaction
When agent, higher feed stock conversion and selectivity of product can be obtained.
The carbon-based material obtained according to the method for the present invention, the distribution of nitrogen therein and oxygen element and metallic element compared with
Uniformly.Such as when being analyzed by X-ray microregion element, in the identical different X-ray microcells of the area on the surface of the carbon-based material, nitrogen member
The coefficient of variation of the content of element and oxygen element and metallic element is below 20%.Wherein, X-ray microcell refers to micro- in progress X-ray
P-block element p observation area selected when analyzing.Wherein, the concept of the coefficient of variation refer to multiple measured values standard deviation and they
Average percentage, i.e. coefficient of variation CV=(standard deviation SD/ average value MN) × 100%.Wherein, X-ray microcell member is carried out
The method of element analysis can measure to obtain according to the method for instrument analysis field routine, such as specific test method may include:
The length direction of carbon-based material such as carbon nanotube with energy depressive spectroscopy along length in the range of 25-250nm is scanned,
Determine that (5 concentration of measurement contain the concentration or content of nitrogen-atoms and oxygen atom and metallic atom on the length direction respectively
Amount), five effective samples are made by same nano-carbon material and are scanned Electronic Speculum-energy spectrum analysis respectively, each sample take 5 not
It is scanned with carbon nanotube, nitrogen-atoms and oxygen atom and metallic atom respectively obtain 25 concentration or content data, calculate
The coefficient of variation of corresponding nitrogen-atoms and oxygen atom and metallic atom.Herein the coefficient of variation refer to the standard deviations of 25 measured values with
The percentage of their average, i.e. coefficient of variation CV=(standard deviation SD/ average value MN) × 100%.In order to preferably reflect
The distributing homogeneity of nitrogen in carbon-based material and oxygen element and metallic element out, it is selected in the analysis of X-ray microregion element
The area on surface of carbon-based material can be 10-250nm2, preferably 20-200nm2。
Wherein, it includes this hair that method of the invention, which obtains having the possible cause of the carbon-based material of above-mentioned pathognomonic feature parameter,
It is that the treatment processes such as hydro-thermal and roasting are combined under specific material variety and material proportion in bright method.
The structural form of the carbon-based material obtained according to the method for the present invention may include carbon nanotube, graphene, fullerene,
At least one of nano carbon particle, active carbon, thin layer graphite, carbon nano-fiber and structural form of Nano diamond.
In another aspect, the purposes the present invention also provides carbon-based material as described above in catalysis oxidation reactions of hydrocarbons.
Wherein, the carbon atom number of the hydrocarbon can be 2-15, and the hydrocarbon includes alkane, alkene and the aromatic hydrocarbon containing alkyl
At least one of；The alkyl contains at least two carbon atoms.Preferably, the hydrocarbon includes butane, 1- butylene, ethylbenzene, third
At least one of alkane, ethane and pentane.
Wherein, carbon-based material as described above can use in oxidation reactions of hydrocarbons as catalyst, and have higher
Hydrocarbon catalyticing oxidation performance.
Wherein, the condition of oxidation reactions of hydrocarbons can be the process conditions of low-carbon alkanes catalytic oxidation routine, such as react
Temperature can be 200-650 DEG C, preferably 300-600 DEG C, more preferably 350-550 DEG C are still more preferably 400-450
DEG C, it can be 0.05-80MPa, preferably 0.1-40MPa, more preferably 0.1-20MPa that the pressure of reaction, which can be pressure, more
Further preferably 0.1-5MPa, the concentration of hydrocarbon can be 1-30 volume %, preferably 1-10 volume %, mole of hydrocarbon and oxygen
Than that can be (0.1-10): 1, preferably (0.2-5): 1, it, can also be containing other to carry in raw material in addition to containing hydrocarbon and oxygen
The balanced gas that gas form introduces, wherein carrier gas can contain nitrogen, group 0 element gas (such as argon gas), CO2With vapor etc.
At least one of.The duration of the reaction can be selected according to the temperature of contact, can use the gas of charging
Volume space velocity come indicate reaction duration.Generally, the volume space velocity of the gas of charging can be 0.1-10000h-1, excellent
It is selected as 1-6000h-1, more preferably 5-5000h-1, further preferably 10-4000h-1。
Present invention be described in more detail by the following examples.In following embodiment and comparative example, if not otherwise specified,
Used reagent is commercially available analytical reagents.Wherein, the phosphorus content without containing oxygen element carbon nanotube is greater than 96 weights
% is measured, ash content is less than 1.5 weight %, specific surface area 168m2/ g is purchased from Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences.
Phosphorus content containing oxygen element carbon nanotube is greater than 95 weight %, and oxygen element content is 1.1 weight %, and ash content is less than 1.2 weights
Measure %, specific surface area 211m2/ g is purchased from Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences.The phosphorus content of graphene is greater than
99 weight %, ash content is less than 0.8 weight %, specific surface area 627m2/ g is purchased from the limited public affairs of Chinese Academy of Sciences Chengdu organic chemistry
Department.
In following embodiment and comparative example, X-ray photoelectron spectroscopic analysis is in Thermo Scientific company
It is carried out on ESCALab250 type x-ray photoelectron spectroscopy.Excitaton source be monochromatization Al K α X-ray, energy 1486.6eV,
Power is 150W.Penetrating used in narrow scan can be 30eV.Base vacuum when analysis test is 6.5 × 10-10mbar.Electronics knot
Closing can be corrected with the peak C1s (284.0eV) of simple substance carbon.The Thermo that Correlation method for data processing is carried in x-ray photoelectron spectroscopy
It carries out on Avantage software, version number V5.926, is carried out in analysis module using sensitivity factor method known to industry
It is quantitative to wait analysis.
In following embodiment and comparative example, thermogravimetric analysis carries out on TA5000 thermal analyzer, and test condition is air gas
Atmosphere, heating rate are 10 DEG C/min, and temperature range is 25 DEG C to 1000 DEG C.
In following embodiment and comparative example, using the ASAP2000 type N of Micromertrics company, the U.S.2Physical absorption
Instrument measurement the specific area.
In following embodiment and comparative example, using the scanning electron microscope equipped with energy depressive spectroscopy (component), (Dutch PHILIPS is public
Take charge of 30 ESEM type scanning electron microscope of XL) measure nano-carbon material (by taking carbon nanotube as an example) surface nitrogen atom and oxygen atom
And the distributing homogeneity of metallic atom, specific test method are as follows: use energy depressive spectroscopy along length in the range of 25-250nm
The length direction of carbon nanotube be scanned, determine nitrogen-atoms and oxygen atom and metallic atom on the length direction respectively
Concentration (measurement 5 concentration), five effective samples be made by same nano-carbon material be scanned Electronic Speculum-power spectrum respectively and divide
Analysis, each sample take 5 different carbon nanotubes to be scanned, nitrogen-atoms and oxygen atom and metallic atom respectively obtain 25 it is dense
Degree evidence calculates the coefficient of variation of corresponding nitrogen-atoms and oxygen atom and metallic atom.The coefficient of variation refers to 25 measurements herein
The percentage of the standard deviation of value and their average, i.e. coefficient of variation CV=(standard deviation SD/ average value MN) × 100%.
Embodiment 1
Under room temperature (25 DEG C), by solid carbon source (carbon nanotube without containing oxygen element), presoma (tetrapropylammonium hydroxide
And sodium hydroxide) and water be stirred 2h, obtain mixed material, wherein the carbon in the solid carbon source and 4 third
The molar ratio of nitrogen in base ammonium hydroxide is 1:0.1, and the molar ratio of the solid carbon source and sodium hydroxide is 1:0.5, institute
The weight ratio for stating solid carbon source and water is 1:10；Mixed material obtained above is placed in polytetrafluoroethyllining lining
Seal autoclave in, in 140 DEG C at autogenous pressures hydro-thermal process for 24 hours, by the solid mistake in the material after hydro-thermal process
Filter is separated and is dried, and dry temperature is 120 DEG C, until the solid being separated by filtration is kept substantially constant weight (drying
Time be 6h), the material after being dried, then by the material after obtained drying under 330 DEG C of maturing temperature, in sky
2h is roasted in gas, then under 430 DEG C of maturing temperature, roasts 2h in air, obtains the carbon-based material of the present embodiment.
Embodiment 2
Under room temperature (25 DEG C), by solid carbon source (carbon nanotube without containing oxygen element), presoma (tetramethylammonium hydroxide
And potassium hydroxide) and water be stirred 1h, obtain mixed material, wherein carbon and tetramethyl in the solid carbon source
The molar ratio of nitrogen in base ammonium hydroxide is 1:0.05, and the molar ratio of the solid carbon source and potassium hydroxide is 1:0.01,
The solid carbon source and the weight ratio of water are 1:5, and mixed material obtained above is placed in polytetrafluoroethyllining lining
Sealing autoclave in, in 180 DEG C at autogenous pressures hydro-thermal process for 24 hours, by the solid in the material after hydro-thermal process
It is separated by filtration and is dried, dry temperature is 120 DEG C, until the solid being separated by filtration is kept substantially constant weight and (does
The dry time is 6h), the material after being dried, then by the material after obtained drying under 300 DEG C of maturing temperature,
2h is roasted in air, then under 400 DEG C of maturing temperature, roasts 2h in air, obtains the carbon-based material of the present embodiment.
Embodiment 3
Under room temperature (25 DEG C), by solid carbon source (carbon nanotube without containing oxygen element), presoma (tetraethyl ammonium hydroxide
And calcium hydroxide) and water be stirred 3h, obtain mixed material, wherein carbon and tetrem in the solid carbon source
The molar ratio of nitrogen in base ammonium hydroxide is 1:5, and the molar ratio of the solid carbon source and calcium hydroxide is 1:2, described solid
Body carbon source and the weight ratio of water are 1:20；Mixed material obtained above is placed in the sealing with polytetrafluoroethyllining lining
In autoclave, in 120 DEG C of hydro-thermal process 48h at autogenous pressures, by the solid filtering point in the material after hydro-thermal process
From and be dried, dry temperature is 120 DEG C, until the solid that is separated by filtration is kept substantially constant weight (when dry
Between be 6h), the material after being dried, then by the material after obtained drying under 350 DEG C of maturing temperature, in air
Roasting 2h roasts 2h then under 450 DEG C of maturing temperature in air, obtains the carbon-based material of the present embodiment.
Embodiment 4
Under room temperature (25 DEG C), by solid carbon source (carbon nanotube without containing oxygen element), presoma (tetrapropylammonium hydroxide
And sodium hydroxide) and water be stirred 5h, obtain mixed material, wherein the carbon in the solid carbon source and 4 third
The molar ratio of nitrogen in base ammonium hydroxide is 1:0.002, and the molar ratio of the solid carbon source and sodium hydroxide is 1:
0.005, the weight ratio of the solid carbon source and water is 1:2；Mixed material obtained above is placed in polytetrafluoroethyl-ne
It, will be in the material after hydro-thermal process in 180 DEG C of hydro-thermal process 12h at autogenous pressures in the sealing autoclave of alkene liner
Solid be separated by filtration and be dried, dry temperature is 120 DEG C, until the solid that is separated by filtration is kept substantially perseverance
It weighs (the dry time is 6h), the material after being dried, then the maturing temperature by the material after obtained drying at 330 DEG C
Under, 2h is roasted in air, then under 380 DEG C of maturing temperature, roasts 2h in air, obtains the carbon substrate of the present embodiment
Material.
Embodiment 5
Under room temperature (25 DEG C), by solid carbon source (carbon nanotube without containing oxygen element), presoma (tetrapropylammonium hydroxide
And sodium hydroxide) and water be stirred 6h, obtain mixed material, wherein the carbon in the solid carbon source and 4 third
The molar ratio of nitrogen in base ammonium hydroxide is 1:50, and the molar ratio of the solid carbon source and sodium hydroxide is 1:10, described
Solid carbon source and the weight ratio of water are 1:100；Mixed material obtained above is placed in polytetrafluoroethyllining lining
Seal autoclave in, in 150 DEG C at autogenous pressures hydro-thermal process for 24 hours, by the solid mistake in the material after hydro-thermal process
Filter is separated and is dried, and dry temperature is 120 DEG C, until the solid being separated by filtration is kept substantially constant weight (drying
Time be 6h), the material after being dried, then by the material after obtained drying under 350 DEG C of maturing temperature, in sky
2h is roasted in gas, then under 450 DEG C of maturing temperature, roasts 2h in air, obtains the carbon-based material of the present embodiment.
Embodiment 6
Carbon-based material is prepared using the method with embodiment 1, unlike, the temperature of hydro-thermal process is 105 DEG C.
Embodiment 7
Carbon-based material is prepared using the method with embodiment 1, unlike, the temperature of hydro-thermal process is 195 DEG C.
Embodiment 8
Carbon-based material is prepared using the method with embodiment 1, unlike, tetrapropylammonium hydroxide is replaced with into hexamethylene diamine
With the equal weight mixtures of n-butylamine, sodium hydroxide is replaced with into sodium carbonate.
Embodiment 9
Carbon-based material is prepared using the method with embodiment 1, unlike, tetrapropylammonium hydroxide is replaced with into diethanol
The equal weight mixtures of amine and aniline, replace with calcium bicarbonate for sodium hydroxide.
Embodiment 10
Carbon-based material is prepared using the method with embodiment 1, unlike carbon nanotube is replaced with etc. to the graphite of weight
Alkene.
Embodiment 11
Carbon-based material is prepared using the method with embodiment 1, unlike, the material after obtained drying is at 330 DEG C
Under maturing temperature, 4h is roasted in air.
Embodiment 12
Carbon-based material is prepared using the method with embodiment 1, unlike, the material after obtained drying is at 430 DEG C
Under maturing temperature, 4h is roasted in air.
Embodiment 13
Carbon-based material is prepared using the method with embodiment 1, unlike, the material after obtained drying is at 500 DEG C
Under maturing temperature, 1h is roasted in air.
Embodiment 14
Carbon-based material is prepared using the method with embodiment 1, unlike, the material after obtained drying is at 210 DEG C
Under maturing temperature, 4h is roasted in air.
Embodiment 15
Carbon-based material is prepared using the method with embodiment 1, unlike, solid carbon source is the carbon nanometer containing oxygen element
Pipe, roasting carry out in argon gas.
Embodiment 16
Carbon-based material is prepared using the method with embodiment 1, unlike, solid carbon source is the carbon nanometer containing oxygen element
Pipe, roasting carry out in air.
Embodiment 17
Carbon-based material is prepared using the method with embodiment 1, unlike, roasting carries out in nitrogen.
Embodiment 18
Carbon-based material is prepared using the method with embodiment 1, unlike, the presoma also contains hydrogen peroxide,
Middle tetrapropylammonium hydroxide and the molar ratio of hydrogen peroxide are 1:0.1.
Embodiment 19
Carbon-based material is prepared using the method with embodiment 10, unlike, the presoma also contains hydrogen peroxide,
Middle tetrapropylammonium hydroxide and the molar ratio of hydrogen peroxide are 1:1.
Embodiment 20
Carbon-based material is prepared using the method with embodiment 15, unlike, the presoma also contains hydrogen peroxide,
Middle tetrapropylammonium hydroxide and the molar ratio of hydrogen peroxide are 1:2.
Comparative example 1
By solid carbon source (carbon nanotube without containing oxygen element), presoma (tetrapropylammonium hydroxide and sodium hydroxide) and
12h is mixed under water normal temperature and pressure, obtains mixed material, wherein carbon and tetrapropyl hydrogen-oxygen in the solid carbon source
Change the molar ratio of the nitrogen in ammonium as 1:0.1, the molar ratio of the solid carbon source and sodium hydroxide is 1:0.5, the solid
Carbon source and the weight ratio of water are 1:10；Mixed material obtained above is dried, dry temperature is 120 DEG C, directly
It is kept substantially constant weight (the dry time is 6h) to the solid being separated by filtration, then the material after being dried is incited somebody to action
Material after the drying arrived roasts 2h under 330 DEG C of maturing temperature in air, then under 430 DEG C of maturing temperature,
2h is roasted in air, using the material after roasting as the carbon-based material of this comparative example.
Comparative example 2
Under room temperature (25 DEG C), by solid carbon source (carbon nanotube without containing oxygen element), presoma (tetrapropylammonium hydroxide
And sodium hydroxide) and water be stirred 6h, obtain mixed material, wherein the carbon in the solid carbon source and 4 third
The molar ratio of nitrogen in base ammonium hydroxide is 1:0.1, and the molar ratio of the solid carbon source and sodium hydroxide is 1:0.5, will
Mixed material obtained above is placed in the sealing autoclave with polytetrafluoroethyllining lining, in 140 DEG C spontaneous
Solid in material after hydro-thermal process is separated by filtration and is dried by hydro-thermal process 24 hours under pressure, dry temperature
It is 120 DEG C, until the solid being separated by filtration is kept substantially constant weight (the dry time is 6h), the object after being dried
Material, then using the material after obtained drying as the carbon-based material of this comparative example.
Testing example 1
The side of method or reference in reference literature (Jian Zhang et al., Science 322 (2008), 73-77)
Method, buy to the obtained carbon-based material of embodiment 1-20 and comparative example 1-2 and as described above containing/receive without containing oxygen element carbon
Mitron carries out elemental analysis and XPS atlas analysis.Wherein, be in x-ray photoelectron spectroscopy 300 DEG C at a temperature of in helium
It is measured after processing 3h in atmosphere.The results are shown in Table 1.
In table 1, XPS map column O1 indicate 533.1-533.5eV within the scope of peak determine oxygen element amount with
The ratio of the amount for the oxygen element that peak within the scope of 531.8-532.2eV determines；O2 is indicated by 529.5- in x-ray photoelectron spectroscopy
The amount for the oxygen element that peak within the scope of 530.8eV determines accounts for the amount for the oxygen element that the peak within the scope of 526.0-535.0eV determines
Ratio × 100 (percent value).The C1 of XPS map column indicates the amount for the carbon that the peak within the scope of 283.8-284.2eV determines
Ratio × 100 (percent value) of the amount of the carbon determined with the peak within the scope of 280.0-294.0eV；C2 indicates 286.2-
The amount for the carbon that the amount for the carbon that peak within the scope of 286.6eV determines and the peak within the scope of 288.6-289.0eV determine it
With amount × 100 (percent value) of the carbon determined with the peak within the scope of 280.0-294.0eV；C3 refers to 286.2-286.6eV
The ratio of the amount for the carbon that the amount for the carbon that peak in range determines and the peak within the scope of 288.6-289.0eV determine.XPS
The amount and the peak within the scope of 395.0-405.0eV that the N1 of map column refers to the nitrogen that the peak within the scope of 398.0-400.5eV determines
Ratio × 100 (percent value) of the amount of determining nitrogen；N2 refers to the nitrogen that the peak within the scope of 400.6-401.5eV determines
Amount and 395.0-405.0eV within the scope of peak determine nitrogen amount ratio × 100 (percent value).W indicates W500/W800
× 100 (percent values).C, N, O and the M of element group in column respectively indicate the element composition of carbon, nitrogen, oxygen and metal.CV was indicated
When X-ray microregion element is analyzed, in the identical different X-ray microcells of the area on the surface of the carbon-based material, nitrogen and oxygen element with
And the coefficient of variation of the content of metallic element, wherein the M of CV column indicates the coefficient of variation of metal element content.
Table 1
Can be seen that according to the analysis test data of embodiment 1-20 in table 1 and comparative example 1-2 may be due to having carried out water
Heat and roasting so that in the XPS map of carbon-based material, the amount for the oxygen element that the peak within the scope of 533.1-533.5eV determines with
The ratio of the amount for the oxygen element that peak within the scope of 531.8-532.2eV determines is in the range of 1-10；By 529.5-530.8eV model
The ratio of the amount for the oxygen element that the peak that the amount for the oxygen element that peak in enclosing determines accounts within the scope of 526.0-535.0eV determines exists
In the range of 0.01-0.1；Within the scope of the amount and 395.0-405.0eV of the nitrogen that peak within the scope of 398.0-400.5eV determines
Peak determine nitrogen amount ratio in the range of 0.5-0.85；400.6-401.5eV the nitrogen that the peak in range determines
The ratio of the amount for the nitrogen that the amount of element and the peak within the scope of 395.0-405.0eV determine is in the range of 0.15-0.5；
The carbon that the amount for the carbon that peak within the scope of 283.8-284.2eV determines and the peak within the scope of 280.0-294.0eV determine
Amount ratio in the range of 0.6-1；The amount and 288.6- for the carbon that peak within the scope of 286.2-286.6eV determines
The carbon that the sum of the amount of carbon that peak within the scope of 289.0eV determines is determined with the peak within the scope of 280.0-294.0eV
The ratio of amount is in the range of 0.02-0.2；The amount and 288.6- for the carbon that peak within the scope of 286.2-286.6eV determines
The ratio of the amount for the carbon that peak within the scope of 289.0eV determines is in the range of 0.3-2；W500/W800For 0.02-0.5；Area
In identical difference X-ray microcell, the coefficient of variation of the content of nitrogen and oxygen element and metallic element is below 20%.
Testing example 2
That buys respectively by the obtained carbon-based material of the embodiment 1-20 of 0.25g and comparative example 1-2 and as described above contains
Oxygen element carbon nanotube and without containing oxygen element carbon nanotube as catalyst, be loaded into universal fixed bed miniature quartz pipe
In reactor, two end seal of miniature quartz pipe reactor has quartz sand, under the conditions of normal pressure and 420 DEG C, by the material (volume of butane
Concentration is 1.98%, and butane and oxygen molar ratio 2:3, Balance Air is nitrogen) total volume air speed be 1000h-1Under reacted, instead
It answers after 8h according to the method in document (322 (2008) 73-77 of Jian Zhang et al., Science), measures conversion of butane
Rate, butadiene selective and total olefin selectivity, the results are shown in Table 2.
Table 2
According to the data of table 2, it is found that the carbon-based material that the present invention obtains can improve hydrocarbon oxygen as catalyst simultaneously
Fluidized dehydrogenation prepares the selectivity and conversion ratio of alkene.Contain carbon, the 0.5-8 weight of 80-98 weight % in preferred carbon-based material
Measure nitrogen, the oxygen element of 1-10 weight % and the metallic element of 0.1-4 weight % of %, the X-ray photoelectricity of the carbon-based material
In sub- power spectrum, the amount for the oxygen element that the peak within the scope of 533.1-533.5eV determines and the peak within the scope of 531.8-532.2eV are determined
Oxygen element amount ratio in the range of 1.2-5 in the case where, further can improve hydrocarbon oxidative dehydrogenation simultaneously and prepare alkene
The selectivity and conversion ratio of hydrocarbon.Also, in the temperature of preferred hydro-thermal process be 120-180 DEG C and maturing temperature is 300-450 DEG C
In the case where, selectivity and conversion ratio that oxidative dehydrogenation prepares alkene can be further improved simultaneously.Meanwhile containing in presoma
When hydrogen peroxide, the selectivity of conversion ratio and alkene can be further improved.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (22)
1. a kind of carbon-based material, it is characterised in that: on the basis of the total weight of the carbon-based material, which contains 60-99
The carbon of weight %, the nitrogen of 0.1-16 weight %, the oxygen element of 0.5-20 weight % and 0.05-8 weight % metal
Element；Wherein, the metallic element includes at least one of alkali metal element and/or alkali earth metal, the carbon-based material
X-ray photoelectron spectroscopy in, the amount and 531.8-532.2eV model of the oxygen element that peak within the scope of 533.1-533.5eV determines
The ratio of the amount for the oxygen element that interior peak determines is enclosed in the range of 1-10, the nitrogen that the peak within the scope of 398.0-400.5eV determines
The ratio of the amount for the nitrogen that the amount of element and the peak within the scope of 395.0-405.0eV determine is in the range of 0.5-0.85.
2. carbon-based material according to claim 1, wherein on the basis of the total weight of the carbon-based material, the carbon-based material
Carbon containing 80-98 weight %, the nitrogen of 0.2-8 weight %, the oxygen element of 1-10 weight % and 0.1-4 weight %
Metallic element, in the x-ray photoelectron spectroscopy of the carbon-based material, oxygen element that the peak within the scope of 533.1-533.5eV determines
The ratio of the amount for the oxygen element that amount is determined with the peak within the scope of 531.8-532.2eV is in the range of 1.2-5.
3. carbon-based material according to claim 2, wherein the carbon-based material contains the carbon of 85-95 weight %, 0.5-
The metallic element of the nitrogen of 6 weight %, the oxygen element of 3-8 weight % and 0.2-3 weight %, the X-ray light of the carbon-based material
In electron spectrum, the amount for the oxygen element that the peak within the scope of 533.1-533.5eV determines and the peak within the scope of 531.8-532.2eV are true
The ratio of the amount of fixed oxygen element is in the range of 1.5-2.5.
4. carbon-based material described in any one of -3 according to claim 1, wherein the x-ray photoelectron energy of the carbon-based material
In spectrum, the amount for the oxygen element that the peak within the scope of 529.5-530.8eV determines accounts for the oxygen that the peak within the scope of 526.0-535.0eV determines
The ratio of the amount of element is in the range of 0.01-0.1.
5. carbon-based material described in any one of -3 according to claim 1, wherein the x-ray photoelectron of the carbon-based material
In power spectrum, what the amount for the nitrogen that the peak within the scope of 400.6-401.5eV determines was determined with the peak within the scope of 395.0-405.0eV
The ratio of the amount of nitrogen is in the range of 0.15-0.5.
6. any one of -3 carbon-based material stated according to claim 1, wherein the x-ray photoelectron spectroscopy of the carbon-based material
In, the carbon that amount and the peak within the scope of 280.0-294.0eV of the carbon that the peak within the scope of 283.8-284.2eV determines determine is first
The ratio of the amount of element is in the range of 0.6-1；The amount and 288.6- for the carbon that peak within the scope of 286.2-286.6eV determines
The carbon that the sum of the amount of carbon that peak within the scope of 289.0eV determines is determined with the peak within the scope of 280.0-294.0eV
The ratio of amount is in the range of 0.02-0.2；The amount and 288.6- for the carbon that peak within the scope of 286.2-286.6eV determines
The ratio of the amount for the carbon that peak within the scope of 289.0eV determines is in the range of 0.3-2.
7. carbon-based material described in any one of -3 according to claim 1, wherein the area phase on the surface of the carbon-based material
In same different X-ray microcells, the coefficient of variation of the content of nitrogen and oxygen element and metallic element each comfortable 20% or less.
8. carbon-based material described in any one of -3 according to claim 1, wherein the W of the carbon-based material500/W800?
In the range of 0.02-0.5；Wherein, W800Refer to the Elevated Temperature Conditions of air atmosphere and 25 DEG C of initial temperature and 10 DEG C/min
Under, slip of the carbon-based material in the weight at 800 DEG C relative to the weight at 400 DEG C, W500Refer to air atmosphere and 25
DEG C initial temperature and 10 DEG C/min Elevated Temperature Conditions under, the carbon-based material is in the weight at 500 DEG C relative at 400 DEG C
Weight slip.
9. carbon-based material described in any one of -3 according to claim 1, wherein the structural form of the carbon-based material includes carbon
The structure of nanotube, graphene, fullerene, nano carbon particle, active carbon, thin layer graphite, carbon nano-fiber and Nano diamond
At least one of form；The metallic element includes at least one of lithium, sodium, potassium, rubidium, caesium, magnesium, calcium, strontium and barium.
10. a kind of method for preparing carbon-based material described in any one of claim 1-9, it is characterised in that: this method packet
Include following steps:
(1) solid carbon source, presoma and water are mixed, obtains mixed material；Wherein, the presoma contains organic alkali source
With inorganic alkali source, organic alkali source includes machine amine and/or quaternary ammonium base；The inorganic alkali source includes the hydroxide of metallic element
The salt of object and/or the metallic element in alkalinity；The metallic element include in alkali metal element and/or alkali earth metal extremely
Few one kind；
(2) the mixed material for obtaining step (1) carries out hydro-thermal process, the material after obtaining hydro-thermal process；And it separates
The solid in material after hydro-thermal process；
(3) solid in the material after hydro-thermal process that step (2) obtains is roasted.
11. according to the method described in claim 10, wherein, in the carbon and organic alkali source in the solid carbon source
The molar ratio of nitrogen is 1:(0.002-50)；The molar ratio of carbon and the inorganic alkali source in the solid carbon source is 1:
(0.005-10)；The weight ratio of carbon and water in the solid carbon source is 1:(1-100).
12. method described in 0 or 11 according to claim 1, wherein carbon and organic alkali source in the solid carbon source
In nitrogen molar ratio be 1:(0.01-10)；The molar ratio of carbon and the inorganic alkali source in the solid carbon source
For 1:(0.01-2)；The weight ratio of carbon and water in the solid carbon source is 1:(5-20).
13. according to the method described in claim 10, wherein, the presoma also contains hydrogen peroxide, in organic alkali source
Nitrogen and hydrogen peroxide molar ratio be 1:(0.01-10).
14. according to the method described in claim 10, wherein, the temperature for carrying out hydro-thermal process is 105-200 DEG C；It carries out at hydro-thermal
The time of reason is 0.5-96h；The temperature of roasting is 200-500 DEG C, and the time of roasting is 0.5-48h.
15. according to the method for claim 14, wherein the temperature for carrying out hydro-thermal process is 120-180 DEG C；The temperature of roasting
It is 300-450 DEG C.
16. according to the method described in claim 10, wherein, roasting carries out in the gas containing oxygen, to contain oxygen
On the basis of the total volume of gas, the content of the oxygen in the gas containing oxygen is 2-25 volume %.
17. according to the method described in claim 10, wherein, the solid carbon source be selected from carbon nanotube, graphene, fullerene,
At least one of nano carbon particle, thin layer graphite, active carbon, carbon nano-fiber and Nano diamond.
18. according to the method described in claim 10, wherein, the organic amine includes aliphatic amine, hydramine, amide, aliphatic cyclic amine
At least one of with aromatic amine；The aliphatic amine be selected from ethamine, n-propylamine, n-butylamine, di-n-propylamine, butanediamine and oneself two
At least one of amine；The hydramine is selected from least one of monoethanolamine, diethanol amine and triethanolamine；The quaternary ammonium base
Selected from least one of tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide；
The amide is selected from formamide, acetamide, propionamide, butyramide, isobutyramide, acrylamide, polyacrylamide, acyl in oneself
At least one of amine, dimethylformamide and dimethyl acetamide；The aliphatic cyclic amine is selected from triethylenediamine, diethylidene
In triamine, hexa, hexamethylene imine, triethylenediamine, cyclic ethylene imines, morpholine, piperazine and cyclohexylamine
It is at least one；The aromatic amine is selected from aniline, diphenylamines, benzidine, o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine, o-methyl-benzene
Amine, m-toluidine, open-chain crown ether, 23 dimethyl aniline, 2,4- dimethylaniline, 2,5- dimethylaniline, 2,6- bis-
Methylaniline, 3,4- dimethylaniline, 3,5- dimethylaniline, 2,4,6- trimethylaniline, o ethyl aniline, N- butylaniline
At least one of with 2,6- diethylaniline；Wherein, the inorganic alkali source include lithium hydroxide, sodium hydroxide, potassium hydroxide,
Rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, carbon
At least one of sour rubidium, cesium carbonate, lithium bicarbonate, sodium bicarbonate, saleratus, rubidium bicarbonate and caesium bicarbonate.
19. the carbon-based material that method described in any one of claim 10-18 is prepared.
20. purposes of the carbon-based material described in any one of claim 1-9 and 19 in catalysis oxidation reactions of hydrocarbons.
21. purposes according to claim 20, wherein the carbon atom number of the hydrocarbon is 2-15, and the hydrocarbon includes alkane, alkene
At least one of hydrocarbon and the aromatic hydrocarbon containing alkyl；The alkyl contains at least two carbon atoms.
22. purposes according to claim 21, wherein the hydrocarbon includes butane, 1- butylene, ethylbenzene, propane, ethane and penta
At least one of alkane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511028862.6A CN106925317B (en) | 2015-12-31 | 2015-12-31 | A kind of carbon-based catalysis material and its synthetic method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511028862.6A CN106925317B (en) | 2015-12-31 | 2015-12-31 | A kind of carbon-based catalysis material and its synthetic method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106925317A CN106925317A (en) | 2017-07-07 |
| CN106925317B true CN106925317B (en) | 2019-07-19 |
Family
ID=59442669
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201511028862.6A Active CN106925317B (en) | 2015-12-31 | 2015-12-31 | A kind of carbon-based catalysis material and its synthetic method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106925317B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109304199B (en) * | 2017-07-28 | 2022-03-11 | 中国石油化工股份有限公司 | Heteroatom-containing nano carbon material, preparation method thereof and thioether oxidation method |
| CN113198520B (en) * | 2021-05-19 | 2022-07-19 | 中国石油大学(华东) | One-pot preparation method of molecular sieve supported palladium carbon catalyst and application of molecular sieve supported palladium carbon catalyst in synthesis of dimethyl carbonate by gas phase method |
| WO2024178611A1 (en) * | 2023-02-28 | 2024-09-06 | 宁德新能源科技有限公司 | Negative electrode active material, secondary battery, and electronic device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101014412A (en) * | 2004-07-16 | 2007-08-08 | 那诺克有限公司 | Catalyst comprising nanocarbon structures for the production of unsaturated hydrocarbons |
| EP2011907B1 (en) * | 2007-07-02 | 2010-01-27 | Centre National De La Recherche Scientifique-CNRS | Process for producing hydrogen gas and carbon nanotubes from catalytic decomposition of ethanol |
| CN103706388A (en) * | 2013-12-30 | 2014-04-09 | 中国科学院化学研究所 | Composite material of nitrogen-doped porous carbon-wrapped carbon nano tube as well as preparation method and application of material |
-
2015
- 2015-12-31 CN CN201511028862.6A patent/CN106925317B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101014412A (en) * | 2004-07-16 | 2007-08-08 | 那诺克有限公司 | Catalyst comprising nanocarbon structures for the production of unsaturated hydrocarbons |
| EP2011907B1 (en) * | 2007-07-02 | 2010-01-27 | Centre National De La Recherche Scientifique-CNRS | Process for producing hydrogen gas and carbon nanotubes from catalytic decomposition of ethanol |
| CN103706388A (en) * | 2013-12-30 | 2014-04-09 | 中国科学院化学研究所 | Composite material of nitrogen-doped porous carbon-wrapped carbon nano tube as well as preparation method and application of material |
Non-Patent Citations (1)
| Title |
|---|
| "Surface-Modified Carbon Nanotubes Catalyze Oxidative Dehydrogenation of n-Butane";Jian Zhang et al.，;《science》;20081003;第322卷;第73-77页以及第1-10页 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106925317A (en) | 2017-07-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105820023B (en) | A kind of method of hydrocarbon oxidation | |
| CN105817250B (en) | A kind of carbon-based material and preparation method thereof | |
| CN105817248B (en) | One kind nano-carbon material containing hetero atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method | |
| Kong et al. | Metal-free catalytic reduction of 4-nitrophenol to 4-aminophenol by N-doped graphene | |
| CN106925317B (en) | A kind of carbon-based catalysis material and its synthetic method | |
| Yang et al. | High graphite N content in nitrogen-doped graphene as an efficient metal-free catalyst for reduction of nitroarenes in water | |
| CN105817239B (en) | It is a kind of carbon-based containing magnesium base composite material and its synthetic method | |
| Huang et al. | Reduced graphene oxide–polyaniline hybrid: preparation, characterization and its applications for ammonia gas sensing | |
| Heydari-Gorji et al. | Degradation of amine-supported CO2 adsorbents in the presence of oxygen-containing gases | |
| JP6867948B2 (en) | Heteroatom-containing nanocarbon material, its production method and use, and hydrocarbon dehydrogenation method | |
| Park et al. | Progressive and invasive functionalization of carbon nanotube sidewalls by diluted nitric acid under supercritical conditions | |
| CN106925270B (en) | A kind of carbon-metal composite material and its synthetic method | |
| Xu et al. | Facile preparation of SBA-15-supported carbon nitride materials for high-performance base catalysis | |
| Luo et al. | Direct hydroxylation of benzene to phenol with molecular oxygen over vanadium oxide nanospheres and study of its mechanism | |
| CN108246338A (en) | A kind of N doping ordered mesopore carbon catalysis material and its preparation method and application | |
| Li et al. | Template-free synthesis of three dimensional porous boron nitride nanosheets for efficient water cleaning | |
| Wang et al. | A novel fluorescence sensing method based on quantum dot-graphene and a molecular imprinting technique for the detection of tyramine in rice wine | |
| CN105817252B (en) | A kind of method of modifying of carbon-based material | |
| Liu et al. | Nitrogen doped nanoflower porous carbon as a nonmetal catalyst for acetylene hydrochlorination | |
| Wang et al. | Octahedron-based redox molecular sieves M-PKU-1 (M= Cr, Fe): A novel dual-centered solid acid catalyst for heterogeneously catalyzed Strecker reaction | |
| JP2008513531A (en) | Method for producing cyclopentanone | |
| CN105820024B (en) | A kind of method of hydrocarbon catalyticing oxidation dehydrogenation | |
| Lu et al. | A molecular brake hoop for the motion of metal atoms inside fullerene cage | |
| Guo et al. | Conjugated polymers with defined chemical structure as model carbon catalysts for nitro reduction | |
| CN109304196A (en) | One kind carbon material containing hetero atom and its preparation method and application and a kind of hydrocarbon oxidative dehydrogenation processes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |