CN113697791A - Defect-rich carbon material and preparation method and application thereof - Google Patents
Defect-rich carbon material and preparation method and application thereof Download PDFInfo
- Publication number
- CN113697791A CN113697791A CN202110864468.5A CN202110864468A CN113697791A CN 113697791 A CN113697791 A CN 113697791A CN 202110864468 A CN202110864468 A CN 202110864468A CN 113697791 A CN113697791 A CN 113697791A
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- Prior art keywords
- carbon
- defect
- carbon material
- rich
- oxidizing
- Prior art date
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 142
- 230000007547 defect Effects 0.000 title claims abstract description 111
- 238000002360 preparation method Methods 0.000 title abstract description 23
- 238000005530 etching Methods 0.000 claims abstract description 62
- 239000007833 carbon precursor Substances 0.000 claims abstract description 59
- 239000000463 material Substances 0.000 claims abstract description 58
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 40
- 230000001590 oxidative effect Effects 0.000 claims abstract description 38
- 230000003647 oxidation Effects 0.000 claims abstract description 32
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 32
- 230000008569 process Effects 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 238000000197 pyrolysis Methods 0.000 claims abstract description 16
- 239000013067 intermediate product Substances 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 14
- 239000000446 fuel Substances 0.000 claims abstract description 8
- 239000007800 oxidant agent Substances 0.000 claims abstract description 7
- 230000000694 effects Effects 0.000 claims abstract description 5
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 23
- 239000001301 oxygen Substances 0.000 claims description 23
- 238000001816 cooling Methods 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 16
- 239000012621 metal-organic framework Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 229920000128 polypyrrole Polymers 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000010411 electrocatalyst Substances 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
- 229910001507 metal halide Inorganic materials 0.000 claims description 4
- 150000005309 metal halides Chemical class 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- 230000002950 deficient Effects 0.000 claims description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 3
- 150000004692 metal hydroxides Chemical class 0.000 claims description 3
- 150000004972 metal peroxides Chemical class 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920000767 polyaniline Polymers 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 31
- 239000003054 catalyst Substances 0.000 abstract description 19
- 238000010438 heat treatment Methods 0.000 abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- 239000000243 solution Substances 0.000 description 29
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 16
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 16
- 229910052573 porcelain Inorganic materials 0.000 description 15
- 238000006722 reduction reaction Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 230000009467 reduction Effects 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 10
- 238000001354 calcination Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- 230000009471 action Effects 0.000 description 8
- 150000002978 peroxides Chemical class 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003763 carbonization Methods 0.000 description 7
- 238000002484 cyclic voltammetry Methods 0.000 description 7
- 230000007246 mechanism Effects 0.000 description 7
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- 239000004246 zinc acetate Substances 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 238000013461 design Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000005539 carbonized material Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 229910021397 glassy carbon Inorganic materials 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- 239000004317 sodium nitrate Substances 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000011865 Pt-based catalyst Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 235000010344 sodium nitrate Nutrition 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- IPLQBXKYVKVYHY-UHFFFAOYSA-N 1h-benzimidazole;zinc Chemical compound [Zn].C1=CC=C2NC=NC2=C1 IPLQBXKYVKVYHY-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 235000005811 Viola adunca Nutrition 0.000 description 2
- 240000009038 Viola odorata Species 0.000 description 2
- 235000013487 Viola odorata Nutrition 0.000 description 2
- 235000002254 Viola papilionacea Nutrition 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- KRQKZTCYIWEUIV-UHFFFAOYSA-N cobalt(2+) 2-methylimidazol-3-ide Chemical compound [Co++].Cc1ncc[n-]1.Cc1ncc[n-]1 KRQKZTCYIWEUIV-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 241000894007 species Species 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 239000004343 Calcium peroxide Substances 0.000 description 1
- 229910020676 Co—N Inorganic materials 0.000 description 1
- HMFHBZSHGGEWLO-SOOFDHNKSA-N D-ribofuranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H]1O HMFHBZSHGGEWLO-SOOFDHNKSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- SPAGIJMPHSUYSE-UHFFFAOYSA-N Magnesium peroxide Chemical compound [Mg+2].[O-][O-] SPAGIJMPHSUYSE-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- PYMYPHUHKUWMLA-LMVFSUKVSA-N Ribose Natural products OC[C@@H](O)[C@@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-LMVFSUKVSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229910001361 White metal Inorganic materials 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- HMFHBZSHGGEWLO-UHFFFAOYSA-N alpha-D-Furanose-Ribose Natural products OCC1OC(O)C(O)C1O HMFHBZSHGGEWLO-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- CAMXVZOXBADHNJ-UHFFFAOYSA-N ammonium nitrite Chemical compound [NH4+].[O-]N=O CAMXVZOXBADHNJ-UHFFFAOYSA-N 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- ZJRXSAYFZMGQFP-UHFFFAOYSA-N barium peroxide Chemical compound [Ba+2].[O-][O-] ZJRXSAYFZMGQFP-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 description 1
- 235000019402 calcium peroxide Nutrition 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229960004995 magnesium peroxide Drugs 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 239000010969 white metal Substances 0.000 description 1
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
-
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Abstract
The invention discloses a defect-rich carbon material and a preparation method and application thereof, wherein the preparation method of the defect-rich carbon material comprises the following steps: (1) preparing or taking a carbon precursor material; (2) heating a carbon precursor material and an oxidation etching agent to 600-1000 ℃ in a protective atmosphere, and reacting for 2-4 h to obtain an intermediate product; wherein, the oxidizing etching agent is a substance which can generate an etching effect on carbon or a substance which can generate an oxidizing substance by pyrolysis or release an oxidizing atmosphere; (3) and (4) carrying out post-treatment on the intermediate product to obtain the defect-rich carbon material. The defect-rich carbon material can be used as a catalyst for fuel cells, can replace the traditional catalyst, greatly improves the catalytic activity, has simple preparation process and simple and convenient operation, and can meet the requirements of different process flows.
Description
Technical Field
The invention relates to the field of carbon-containing catalytic materials, in particular to a defect-rich carbon material and a preparation method and application thereof.
Background
The fuel cell is a novel power generation device which directly converts chemical energy generated by oxidation reduction of fuel and oxidant into electric energy, and has the advantages of environmental protection, high energy conversion efficiency, quick start and close and the like. However, the development of fuel cells is still limited by problems such as a slow kinetics of the cathode Oxygen Reduction Reaction (ORR) and a limited practical energy density. The oxygen reduction catalyst of the air cathode plays a crucial role in the performance of the battery, and largely determines the energy efficiency of the battery as a whole. Designing and developing efficient oxygen reduction catalysts has become a key technology and research hotspot for improving the electrochemical performance of fuel cells.
The oxygen reduction electrocatalyst is one of the key materials of the fuel cell, and the current commercial oxygen reduction catalyst mainly uses Pt/C, but the Pt resource is limited, the price is high, and the stability of the oxygen reduction electrocatalyst needs to be further improved. The defective carbon material has the advantages of low cost and excellent stability, and is a novel oxygen reduction catalyst material with great potential. However, the catalytic activity of the carbon-based catalyst is still far from that of commercial Pt/C, and the design of a synthesis strategy with industrialization and universality to improve the catalytic activity of the carbon material is a research and development hotspot of the current carbon-based catalyst.
At present, a carbon material is obtained by mainly calcining a carbon precursor at high temperature, and the carbon material with a certain catalytic action is obtained by adjusting and controlling the defects of a derived carbon material by changing the composition and the structure of the precursor. In addition, N doping is an effective way for improving the catalytic activity of the carbon material at present. However, the conventional synthesis of the N-doped carbon material is to mix and calcine a nitrogen source and a carbon source, so that the exposure of active nitrogen is difficult to realize, and the catalytic activity is not as expected. Meanwhile, in the traditional carbon material synthesis process, different carbon precursors (namely different types of nitrogen sources and carbon sources) are adopted, so that the carbon materials derived from the carbonized carbon materials are different in nitrogen defect form, but the catalytic performance of the carbon materials is difficult to greatly improve due to the lack of defect sites with high-efficiency catalytic activity. Therefore, compared with the carbon material obtained by deriving carbon precursors with different structure types, the method for developing a universal carbon-based defect promotion strategy to improve the oxygen reduction catalytic activity of the carbon-based material is a research focus of the current catalyst development.
Disclosure of Invention
The invention provides a defect-rich carbon material and a preparation method and application thereof, which are used for solving the technical problems of low catalytic activity and complicated design and synthesis steps of the existing carbon material.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for preparing a defect-rich carbon material, comprising the steps of:
(1) preparing or taking a carbon precursor material which can form reducing carbon under high-temperature pyrolysis;
(2) carrying out high-temperature pyrolysis on the carbon precursor material and an oxidation etching agent in a protective atmosphere to form carbon vacancies and/or abundant defective carbon, and cooling to obtain an intermediate product; wherein, the oxidizing etching agent can generate etching action on carbon or generate oxidizing substances or release oxidizing atmosphere substances in the pyrolysis process;
(3) and carrying out post-treatment on the intermediate product to obtain the defect-rich carbon material.
The design idea of the technical scheme is that the oxidizing etchant and the carbon precursor material are heated together, the oxidizing etchant etches the precursor in the process, or the oxidizing etchant is pyrolyzed to generate oxidizing substances or oxidizing gas to etch the precursor locally, and the main action principle of the oxidizing etchant is as follows: the precursor gradually begins to be carbonized and reformed to form graphitized carbon material in the pyrolysis process, while the graphitic carbon has stronger reducibility, and because the oxidizing etching agent has strong oxidizing property, or oxidizing substances or oxidizing gases generated by the oxidizing etching agent in the pyrolysis process and carbon with reducibility have partial redox reaction (C + O)oxy→ CO + Ored, oxy and Ored are oxidizing species, reduced species, respectively), local carbon is etched out in the form of CO, leaving a large number of carbon vacancies and forming abundant defect carbon. Compared with the prior art that the structure of the carbon precursor needs to be designed and synthesized in advance for forming the carbon defect sites, the method is suitable for most carbon precursor materials, can greatly avoid the difficulty of structural design and synthesis of the precursor, and has practicability and universality.
As a further preferable mode of the above technical solution, the oxidizing etchant includes a metal oxygen-containing compound, a metal halide, a nonmetal compound, and a halogen simple substance. Making
As a further preferable mode of the above technical solution, the oxidizing etchant includes at least one of a metal oxygen-containing compound, a metal halide and a simple substance of halogen; the metal oxygen-containing compound includes at least one of a metal oxide, a metal hydroxide, a metal peroxide, a strongly oxidizing salt, a carboxylate, and a nitrate. The three types of oxidation etching agents can generate oxidation etching effect on carbon or can generate etching effect on the carbon material per se in the pyrolysis process, and the oxidation etching agents are convenient to remove after pyrolysis, complex impurity removal processes are not required to be introduced, loss of active sites of the carbon material matrix is avoided, and meanwhile, the oxidation etching agents are low in cost, easy to obtain, suitable for mass production and beneficial to industrialization. The oxidizing and etching agent capable of directly etching the carbon precursor comprises metal oxides (sodium oxide, potassium oxide, magnesium oxide, calcium oxide, zinc oxide, iron oxide and the like) and metal hydroxides (potassium hydroxide, sodium hydroxide, iron hydroxide and the like). The oxidizing etchant for etching a carbon precursor by generating an oxidizing substance by pyrolysis includes metal peroxides (sodium peroxide, magnesium peroxide, barium peroxide, calcium peroxide, etc.), strongly oxidizing salts (potassium permanganate, potassium dichromate, potassium chlorate, etc.), carboxylates (zinc acetate, sodium acetate, etc.), nitrates (sodium nitrate, potassium nitrate, zinc nitrate, copper nitrate, cobalt nitrate, sodium nitrite, etc.), metal halides (including sodium chloride, potassium chloride, sodium bromide, sodium iodide, potassium bromide, zinc chloride, zinc bromide, iron chloride, etc.), non-metallic compounds (hydrogen peroxide, peracetic acid, ammonium chloride, ammonium nitrate, ammonium nitrite, etc.), elemental halogens (liquid bromine, elemental iodine, etc.).
As a further optimization of the technical scheme, the addition amount of the oxidation etching agent in the step (2) is 0.2-8 times of the mass of the precursor material. The adding proportion of the oxidation etching agent is different according to the carbon content of the precursor, and the oxidation etching agent can effectively carry out partial etching on a small amount of carbon to construct carbon intrinsic defect sites under the premise of a certain carbonization yield within the proportion range.
In a further preferred embodiment of the present invention, the carbon precursor material is a carbon precursor material in which carbon defect sites are not formed
As a further preferable mode of the above aspect, the carbon precursor material isThe nitrogen-containing material contains nitrogen elements. The carbon precursor material containing nitrogen element can introduce extrinsic defects into the carbon material by doping N element, so that the carbon material has intrinsic defects and extrinsic defects at the same time, and the carbon material is promoted to enhance O by virtue of nonuniform electron cloud density distribution and change of space curvature of the carbon layer caused by N doping and intrinsic carbon defects2The adsorption acting force of the carbon material is adjusted, the adsorption energy of the oxygen-containing intermediate in the oxygen reduction process is adjusted to promote the process of the oxygen reduction reaction, the oxygen reduction catalytic performance of the carbon material is greatly improved, meanwhile, N is doped into the carbon network structure in the pyrolysis process of the N-containing precursor, the N-doped and defect carbon cooperative sites are formed, and the defect site density of the carbon material is further improved by combining the carbon defect left by the oxidation etching.
As a further preferred aspect of the above technical solution, the carbon precursor material includes at least one of a metal-organic framework complex and a carbon-containing polymer. Compared with other common carbon precursor materials (such as common carbon sources of glucose, melamine, citric acid, ribose and the like), the two carbon precursor materials have a certain thermal stability structure, are easy to carbonize to form a carbon material, have no impurities or only have a small amount of impurities which are easy to remove after carbonization, can obtain the carbon material with a richer pore structure and a larger specific surface area after calcination, and are beneficial to the promotion of catalytic activity.
As a further preferred aspect of the above technical solution, the metal organic framework complex is one or a combination of several of a ZIF series complex, a CPL series complex, an MIL series complex, a hexamethylenetetramine complex, and a metal phthalocyanine complex, and such a precursor has a high carbonization yield, and can avoid excessive oxidation etching to bring a large amount of carbon loss, thereby obtaining a carbon material with a high yield.
As a further optimization of the technical scheme, the carbon-containing polymer is one or a combination of more of polypyrrole, polyaniline, polyacrylamide and polyacrylic acid, and the precursor is simple to prepare, high in carbonization yield and easy to obtain a carbon material.
As a further preferred aspect of the above technical solution, the post-treatment in step (3) includes soaking, washing and filtering operations.
Based on the same technical concept, the invention also provides a defect-rich carbon material which is prepared by the preparation method of the technical scheme.
The design idea of the technical scheme is that the carbon material prepared by the method can be used for replacing the traditional commercial noble metal Pt-based catalyst, the catalytic activity is greatly improved (the maximum half-wave potential lifting amplitude can reach more than 200 mV), the catalytic performance and the cycle stability of the carbon material are superior to those of a Pt/C catalytic material, the production cost is low, and the carbon material has a wide market prospect.
Based on the same technical concept, the invention also provides an application of the defect-rich carbon material or the defect-rich carbon material prepared by the preparation method, and the defect-rich carbon material is applied to a fuel cell as an electrocatalyst.
Compared with the prior art, the invention has the advantages that:
(1) according to the preparation method, the carbon precursor is etched through the oxidizing atmosphere/oxide generated in the pyrolysis process of the oxidant, so that the defect sites of the carbon material, particularly carbon intrinsic defects such as carbon vacancies, carbon edges and the like, are promoted; meanwhile, the catalytic activity of the carbon-based catalyst is greatly improved by utilizing N-doped defects generated in the pyrolysis process of the N-containing carbon precursor in cooperation with intrinsic defect sites and N-doped defect sites; the preparation process is simple, the operation is simple and convenient, the structure of the carbon precursor and the type of the oxidant can be adjusted according to the requirements, the method is suitable for most carbon precursor materials, the difficulty in structural design and synthesis of the precursor can be greatly avoided, the practicability and universality are realized, the operation flexibility is strong, and the method can be suitable for the requirements of different process flows;
(2) the defect carbon material prepared by the preparation method can be used for replacing the traditional commercial noble metal Pt-based catalyst, the catalytic activity of the defect carbon material is greatly improved (the maximum half-wave potential lifting amplitude can reach more than 200 mV), and the defect carbon material has better catalytic performance and cycle stability than Pt/C catalytic materials.
Drawings
FIG. 1 is a scanning electron micrograph of a defect-rich carbon material of example 1;
FIG. 2 is a comparison of linear cyclic voltammograms of the defect-rich carbon material of example 1.
FIG. 3 is a scanning electron micrograph of the defect-rich carbon material of example 2;
FIG. 4 is a comparison of linear cyclic voltammograms of the defect-rich carbon material of example 2;
FIG. 5 is a scanning electron micrograph of the defect-rich carbon material of example 3;
FIG. 6 is a comparison of linear cyclic voltammograms of the defect-rich carbon material of example 3; (ii) a
FIG. 7 is a scanning electron micrograph of the defect-rich carbon material of example 3;
FIG. 8 is a comparison of linear cyclic voltammograms of the defect-rich carbon material of example 4;
FIG. 9 is a scanning electron micrograph of the defect-rich carbon material of example 5;
FIG. 10 is a comparison of linear cyclic voltammograms of the defect-rich carbon material of example 5;
FIG. 11 is a linear cyclic voltammogram of a commercial Pt/C catalyst.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1:
in the preparation method of the defect-rich carbon material, in the embodiment, a metal organic framework complex of zinc-benzimidazole (Zn-BZIM) is used as a carbon precursor material, and an oxidation etching strategy is used to promote defect sites of the Zn-BZIM derived carbon material so as to promote the electrocatalysis performance of the Zn-BZIM derived carbon material, and the specific preparation method is as follows:
(1) preparing a carbon precursor material: dissolving 10mmol of zinc nitrate in 100mL of methanol solution, dissolving 20mmol of benzimidazole in 100mL of methanol solution, mixing the two solutions after complete dissolution, stirring for 12h at room temperature, and standing for 2h at normal temperature to obtain white complex precipitate. Carrying out vacuum filtration on the suspension, washing the suspension with an alcoholic solution for three times, and drying the suspension at 60 ℃ for 12 hours to obtain a white metal organic framework complex of zinc-benzimidazole (Zn-BZIM);
(2) placing 300mg of Zn-BZIM as carbon precursor material in a porcelain boat, placing 600mg of sodium chloride (NaCl) as oxidation etching agent in the porcelain boat, placing in a sealed tube furnace, and performing Ar/H oxidation treatment in the presence of Ar/H2Heating to 900 ℃ from room temperature at the speed of 5 ℃/min under the atmosphere, keeping the temperature for 2 hours, and naturally cooling to obtain an intermediate product;
(3) and soaking the obtained intermediate product in water overnight, washing and filtering to obtain the product, namely the defect-rich carbon material ON/C-1.
Putting 300mg of Zn-BZIM obtained in the step (1) as a carbon precursor into a porcelain boat, and performing Ar/H2And heating the mixture to 900 ℃ from room temperature at the speed of 5 ℃/min in the atmosphere, keeping the temperature for 2 hours, naturally cooling and cooling to obtain an N-doped carbon material N/C-1, wherein the N-doped carbon material obtained without oxidation etching is used for comparing with the defect-rich carbon material ON/C-1 in the embodiment.
Subjecting the obtained defect-rich carbon material ON/C-1 to field emission scanning electron microscope (SEM, JSM-7610F, JEOL)TM) The grain size and the micro morphology of the metal organic framework are observed, a scanning electron microscope image of the metal organic framework is shown in figure 1, and the figure shows that the metal organic framework is oxidized and etched by halide ON the basis of the Zn-BZIM, and the ON/C-1 is changed into a printed cake-shaped structure after the metal organic framework is oxidized, etched and calcined.
The electrochemical performance test of the obtained defect-rich carbon material ON/C-1, the carbon material N/C-1 obtained without the peroxide etching and commercial 20 wt% Pt/C is carried out, and the test method is as follows: 6mg of the catalyst material is put into a 2mL small centrifugal tube, 0.98mL of absolute ethyl alcohol is accurately transferred into the small centrifugal tube by a 1mL pipette, and finally 20 mu L of 5% Nafion emulsion is absorbed into the centrifugal tube by a liquid transfer gun. And (4) carrying out ultrasonic treatment for one hour until the solution is uniformly dispersed without obvious particle precipitation. The circular ring electrode of the rotating disc is a glassy carbon electrode with the diameter of 5mm, and the glassy carbon electrode needs to be subjected to Al treatment in advance2O3Polishing with polishing powder, washing with distilled water, and drying with a piece of lens wiping paper. And (3) absorbing 8 mu L of uniformly dispersed catalyst sample by using a pipette during testing, uniformly and flatly paving the catalyst sample in the center of the polished glassy carbon electrode, and naturally airing to obtain the working electrode.An NOVA2.0 electrochemical workstation is used for carrying out electrochemical performance test, a three-electrode system is adopted for testing, a reference electrode is an Ag/AgCl electrode, a counter electrode is a carbon rod, and a working electrode is a glassy carbon electrode loaded with a catalyst. After the three-electrode system is assembled, in order to ensure the saturated oxygen condition, oxygen needs to be introduced into 0.1MKOH electrolyte for half an hour in advance, and then linear cyclic voltammetry scanning is carried out, wherein the scanning interval is 0.20 to-0.90 Vvs.Ag/AgCl, and the scanning speed is 10mV s-1。
The test results of the defect-rich carbon material ON/C-1 and the carbon material N/C-1 obtained without the peroxide etching are shown in FIG. 2, and the test results of the commercial 20 wt% Pt/C material are shown in FIG. 11, and it can be seen that the defect-rich carbon material has excellent oxygen reduction catalytic activity, which is superior to the carbon material N/C-1 obtained without the peroxide etching and the commercial 20 wt% Pt/C performance, and the carbon material with high activity can be obtained by the method, and the action mechanism is mainly that the halide can generate hydrogen chloride acid gas during the calcination process, partially etches the precursor, causes the formation of carbon defects, and exposes rich defect sites. The main catalytic performance of the catalyst formed by oxidation, etching and carbonization mainly comes from the synergistic action sites of carbon intrinsic defects and N-doped extrinsic defects.
Example 2:
in the preparation method of the defect-rich carbon material, in the embodiment, a zinc-2-methylimidazole (ZIF-8) metal organic framework complex is used as a carbon precursor material, and an oxidation etching strategy is used for improving defect sites of a ZIF-8 derived carbon material to improve the electrocatalysis performance of the carbon precursor material, and the preparation method specifically comprises the following steps:
(1) preparing a carbon precursor material: dissolving 20mmol of zinc nitrate in 100mL of methanol solution, dissolving 80mmol of 2-methylimidazole in 100mL of methanol solution, mixing the two solutions after complete dissolution, stirring for 12h at room temperature, and standing for 24h at normal temperature to obtain white complex precipitate. Centrifuging the solution three times at 8000r/min, washing with methanol solution three times, and drying at 60 deg.C for 12 hr to obtain white metal-organic framework complex of zinc-2-methylimidazole (ZIF-8);
(2) taking 400mg of the obtained ZIF-8 as a carbon precursor material, placing the carbon precursor material in a porcelain boat, and taking 200mg of sodium nitrite (NaNO)2) Heating the ceramic boat serving as an oxidation etching agent to 900 ℃ from room temperature at the speed of 5 ℃/min in a high-temperature tube furnace protected by Ar, keeping the temperature for 2 hours, and naturally cooling to obtain an intermediate product;
(3) and soaking the obtained intermediate product in an aqueous solution overnight to remove residual metal oxide impurities, and filtering, washing and drying to obtain the defect-rich carbon material ON/C-2.
And (2) placing 400mg of ZIF-8 obtained in the step (1) as a carbon precursor in a porcelain boat, heating the carbon precursor to 900 ℃ from room temperature at a speed of 5 ℃/min under Ar atmosphere, keeping the temperature for 2h, naturally cooling and cooling to obtain an N-doped carbon material N/C-2, wherein the N-doped carbon material obtained without oxidation etching is used for comparing with the defect-rich carbon material ON/C-2 in the embodiment.
Subjecting the obtained defect-rich carbon material ON/C-2 to field emission scanning electron microscope (SEM, JSM-7610F, JEOL)TM) The grain size and the micro morphology of the carbon material are observed through detection, a scanning electron microscope image of the carbon material is shown in figure 3, and the scanning electron microscope image shows that the carbon material carbonized by ZIF-8 presents an obvious fold lamellar structure under the action of the oxidation etching of nitrite.
The obtained defect-rich carbon material ON/C-2 and the carbon material N/C-2 obtained without the peroxide etching were subjected to electrochemical performance tests in accordance with the test method in example 1.
The test results for the defect-rich carbon material ON/C-2 and carbon material N/C-2 obtained without the peroxide etching are shown in FIG. 4, from which it can be seen that, the defect-rich carbon material has excellent oxygen reduction catalytic activity, compared with carbon material N/C which is not subjected to peroxide etching, ON/C-2 shows more positive half-wave potential and larger limiting current and is superior to commercial 20 wt% Pt/C, and the catalytic activity of the whole material can be improved by the method, the action mechanism of the method mainly lies in the strong oxidizing property of nitrite, a local carbon precursor is oxidized to form abundant carbon defect sites in the mixing and calcining process of the nitrite and the carbon precursor, and the calcined material has abundant carbon defect structures and exposes abundant active sites, so that the defect sites of the carbon material are improved, and the catalytic performance is greatly improved.
Example 3:
in the preparation method of the defect-rich carbon material of the embodiment, polypyrrole is used as a carbon precursor material, and the specific preparation method is as follows:
(1) preparing a carbon precursor material: 40mmol of pyrrole monomer was dissolved in 300mL of an alcohol/water mixture (ethanol: water: 1), and 40mmol of persulfuric acid was dissolved in 25mL of water. Slowly and dropwise adding the ammonium persulfate solution into the pyrrole solution, and stirring for 12 hours in an ice bath environment to obtain a dark green suspension solution. And filtering, washing and drying the obtained suspension to obtain dark green powder, namely the polypyrrole Ppy.
(2) Placing 300mg of the Ppy in a big porcelain boat, and taking 150mg of sodium nitrate (NaNO)3) And (2) placing the small porcelain boat filled with sodium nitrate into the large porcelain boat filled with Ppy, placing the small porcelain boat in a high-temperature tube furnace protected by Ar, heating the small porcelain boat to 900 ℃ from room temperature at a speed of 10 ℃/min, keeping the temperature for 3 hours, and naturally cooling to obtain black powder which is the defect-rich carbon material ON/C-3 without subsequent treatment.
And (2) placing 300mg of Ppy obtained in the step (1) as a carbon precursor in a porcelain boat, heating the Ppy to 900 ℃ from room temperature at a speed of 10 ℃/min under Ar atmosphere, keeping the temperature for 2h, naturally cooling and cooling to obtain an N-doped carbon material N/C-3, wherein the N-doped carbon material obtained without oxidation etching is used for comparing with the defect-rich carbon material ON/C-3 of the embodiment.
Subjecting the obtained defect-rich carbon material ON/C-3 to field emission scanning electron microscope (SEM, JSM-7610F, JEOL)TM) And (3) detecting, observing the grain size and the microstructure, wherein a scanning electron microscope image of the material is shown in figure 5, and oxidizing, etching and calcining the material in a polypyrrole precursor to obtain a polypyrrole carbonized material with small particles, wherein the morphology structure of the polypyrrole carbonized material is consistent with that of polypyrrole obtained by direct carbonization.
And carrying out electrochemical performance test ON the obtained defect-rich carbon material ON/C-3 and the carbon material N/C-3 obtained without peroxide etching, wherein the test method is consistent with that in the embodiment 1.
The results of testing the defect-rich carbon material ON/C-3 and the carbon material N/C-3 obtained without the hydrogen peroxide etching are shown in FIG. 6, from which it can be seen that the catalyst shows a half-wave potential rise of nearly 200mV and a larger limiting current compared to the material without the hydrogen peroxide etching, and is comparable to the commercial 20 wt% Pt/C performance. The action mechanism is mainly that a large amount of NO and O are generated in the calcining process through sodium nitrate2And the carbon material with rich carbon defects is obtained by oxidizing, etching and carbonizing the polypyrrole precursor in the calcining process by using the etching gas with the oxidizing property. The carbon intrinsic defect is introduced by the method, and the carbon intrinsic defect is cooperated with the N-doped defect sites, so that the catalytic activity of the carbon material can be greatly improved.
Example 4:
in the preparation method of the defect-rich carbon material, in the embodiment, a zinc-2-methylimidazole (ZIF-8) metal organic framework complex is used as a carbon precursor material, and zinc acetate is used for oxidation etching, and the specific preparation method is as follows:
(1) preparing a carbon precursor material: dissolving 50mmol of zinc nitrate in 100mL of methanol solution, dissolving 200mmol of 2-methylimidazole in 100mL of methanol solution, mixing the two solutions after complete dissolution, stirring for 12h at room temperature, and standing for 24h at normal temperature to obtain white complex precipitate. Filtering the suspension, washing with methanol solution for three times, and drying at 60 deg.C for 12 hr to obtain white zinc-2-methylimidazole (ZIF-8) metal-organic framework complex;
(2) 500mg of the obtained ZIF-8 was used as a carbon precursor material with 500mg of zinc acetate (Zn (CH)3COO)2) Mixing with ethanol solution, stirring and drying ethanol at 60 deg.C to obtain mixture of ZIF-8 and zinc acetate, and adding the mixture into N2Heating the mixture to 900 ℃ from room temperature at the speed of 7 ℃/min in a protected high-temperature tube furnace, keeping the temperature for 2 hours, and naturally cooling to obtain an intermediate product;
(3) soaking the intermediate product in 0.5mol/L sulfuric acid solution overnight, filtering, washing and drying to obtain the product ON/C-4 material.
Putting 500mg of ZIF-8 obtained in the step (1) as a carbon precursor in a porcelain boat, and adding N2And heating the mixture to 900 ℃ from room temperature at the speed of 7 ℃/min in the atmosphere, keeping the temperature for 2 hours, naturally cooling and cooling to obtain an N-doped carbon material N/C-4, wherein the N-doped carbon material obtained without oxidation etching is used for comparing with the defect-rich carbon material ON/C-4 in the embodiment.
Subjecting the obtained defect-rich carbon material ON/C-4 to field emission scanning electron microscope (SEM, JSM-7610F, JEOL)TM) The grain size and the micro morphology of the carbon sheet are observed through detection, a scanning electron microscope image of the carbon sheet is shown in FIG. 7, and it can be seen from the image that the carbon sheet with a sheet structure and a rich pore structure is obtained after zinc acetate is mixed in ZIF-8 for oxidation, etching and calcination.
And carrying out electrochemical performance test ON the obtained defect-rich carbon material ON/C-4 and the carbon material N/C-4 obtained without peroxide etching, wherein the test method is consistent with that in the embodiment 1.
The test results for the defect-rich carbon material ON/C-4 and the carbon material N/C-4 obtained without the hydrogen peroxide etching are shown in FIG. 8, from which it can be seen that the defect-rich carbon material has excellent oxygen reduction catalytic activity, and from which it can be seen that the catalyst shows a more positive half-wave potential and a larger limiting current than the material N/C-4 without the hydrogen peroxide etching. The action mechanism of the method is mainly that the oxidation etching mechanism of zinc sulfate is that zinc acetate is converted into ZnO in the heating process and simultaneously a large amount of CO is released2CO while making pore on the material2The carbon material reacts with ZnO and a local carbon precursor to generate CO and Zn simple substances, so that local carbon defects are caused, the defect site density of the carbon material is improved, and the improvement of the catalytic activity of the carbon material can be realized through zinc acetate oxidation etching.
Example 5:
in the preparation method of the defect-rich carbon material, in the embodiment, a zinc/cobalt-2-methylimidazole (Zn/Co-BZIF) metal organic framework complex is used as a carbon precursor material, and sodium bromide is used for oxidation etching to obtain a Co-N Co-doped carbon material, and the specific preparation method is as follows:
(1) preparing a carbon precursor material: dissolving 47.5mmol of zinc nitrate and 2.5mmol of cobalt nitrate in 100mL of methanol, dissolving 200mmol of 2-methylimidazole in 100mL of methanol solution, mixing the two solutions after complete dissolution, stirring at room temperature for 6h, and standing at room temperature for 24h to obtain a blue-violet complex precipitate. Filtering the suspension, washing with methanol solution for three times, and drying at 60 deg.C for 12 hr to obtain blue-violet zinc/cobalt-2-methylimidazole (Zn/Co-BZIF) metal-organic framework complex;
(2) putting 200mg of Zn/Co-BZIF obtained as a carbon precursor material into a porcelain boat, and taking 100mg of iodine simple substance (I)2) As an oxidizing etchant in a porcelain boat at Ar/H2Heating the mixture to 800 ℃ from room temperature at the speed of 5 ℃/min in a protected high-temperature tube furnace, keeping the temperature for 2 hours, and naturally cooling to obtain an intermediate product;
(3) soaking the intermediate product in 0.5mol/L sulfuric acid solution overnight, filtering, washing and drying to obtain the defect-rich carbon material OCo, N/C.
Putting 200mg of Zn/Co-BZIF obtained in the step (1) as a carbon precursor into a porcelain boat, and putting the carbon precursor in Ar/H2Heating the mixture to 800 ℃ from room temperature at a speed of 5 ℃/min in the atmosphere, keeping the temperature constant for 2 hours, naturally cooling and cooling the mixture, soaking the mixture in a 0.5mol/L sulfuric acid solution for a while, filtering, washing and drying the mixture to obtain Co and N Co-doped carbon materials Co and N/C, wherein the Co and N doped carbon materials obtained without oxidation etching are used for comparing with the defect-rich carbon materials OCo and N/C in the embodiment.
Subjecting the obtained defect-rich carbon material OCo, N/C to field emission scanning electron microscope (SEM, JSM-7610F, JEOL)TM) And (3) detecting, and observing the grain size and the microstructure of the carbonized material, wherein a scanning electron microscope image of the carbonized material is shown in FIG. 9, and the carbonized material with a cubic structure is obtained by performing oxidation etching calcination in a Zn/Co-BZIF precursor.
The obtained defect-rich carbon material OCo, N/C and the carbon material Co, N/C obtained without the hydrogen peroxide etching were subjected to electrochemical performance tests, and the test methods were the same as those in example 1.
The results of testing the defect-rich carbon material OCo, N/C and the carbon material Co, N/C obtained without the hydrogen peroxide etching are shown in FIG. 10, from which it can be seen that the defect-rich carbon material shows a more positive half-wave potential rise and a larger limiting current than the material without the hydrogen peroxide etching, and is comparable to the commercial 20 wt% Pt/C performance. The action mechanism of the method is mainly characterized in that iodine simple substance is combined with hydrogen in argon/hydrogen mixed gas to form corrosive acid gas hydroiodic acid, a carbon precursor is etched, the structure of the carbon precursor is damaged to generate a large number of carbon defect sites in the carbonization process, the abundant carbon defect sites are constructed through an oxidation etching mechanism, so that the active sites of the material are greatly improved, the adsorption force of the material on oxygen is enhanced, and the catalytic activity of the carbon material can be greatly improved.
The embodiment shows that the carbon material prepared by the method can completely replace the current commercial noble metal Pt-based catalyst, the preparation method obviously improves the catalytic activity of carbon materials derived from different carbon precursors, the carbon intrinsic defect sites constructed by the method are cooperated with the extrinsic defect sites generated by N doping to greatly improve the catalytic activity of the material, and the method has universality, practicability and economy. Meanwhile, the selection of the oxidant and the carbon precursor is flexible, a proper oxidation etching strategy can be selected according to actual requirements and a process flow, the cost of the oxygen reduction catalyst is reduced, the process flow is simplified, the manufacturing cost of the air cathode is further reduced, and the method has a wide market prospect.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. Modifications and variations that may occur to those skilled in the art without departing from the spirit and scope of the invention are to be considered as within the scope of the invention.
Claims (10)
1. A method for preparing a defect-rich carbon material, comprising the steps of:
(1) preparing or taking a carbon precursor material which can form reducing carbon under high-temperature pyrolysis;
(2) carrying out high-temperature pyrolysis on the carbon precursor material and an oxidation etching agent in a protective atmosphere to form carbon vacancies and/or abundant defective carbon, and cooling to obtain an intermediate product; wherein, the oxidizing etching agent is a substance capable of generating an etching effect on carbon or a substance capable of generating an oxidizing substance or releasing an oxidizing atmosphere in a pyrolysis process;
(3) and carrying out post-treatment on the intermediate product to obtain the defect-rich carbon material.
2. The method for producing a defect-rich carbon material as claimed in claim 1, wherein the oxidizing etchant comprises at least one of a metal oxygen-containing compound, a metal halide and an elemental halogen.
3. The method for producing a defect-rich carbon material as claimed in claim 2, wherein the metal oxygen-containing compound comprises at least one of a metal oxide, a metal hydroxide, a metal peroxide, a strong oxidizing salt, a carboxylate and a nitrate.
4. The method for preparing a defect-rich carbon material as claimed in claim 1, wherein the amount of the oxidizing etchant added in step (2) is 0.2-8 times the mass of the precursor material.
5. The method for producing a defect-rich carbon material as claimed in claim 1, wherein the pyrolysis in the step (2) is carried out at a temperature of 600 to 1000 ℃ for 2 to 4 hours.
6. The method for producing a defect-rich carbon material according to any one of claims 1 to 5, wherein the carbon precursor material is a carbon precursor material in which carbon defect sites are not formed.
7. The method of producing a defect-rich carbon material as claimed in claim 6, wherein the carbon precursor material contains nitrogen element, and the carbon precursor material includes at least one of a metal-organic framework complex and a carbon-containing polymer.
8. The method for producing a defect-rich carbon material as claimed in claim 7, wherein the metal-organic framework complex is one or a combination of several of a ZIF series complex, a CPL series complex, an MIL series complex, a hexamethylenetetramine complex and a metal phthalocyanine complex; the carbon-containing polymer is one or a combination of more of polypyrrole, polyaniline, polyacrylamide and polyacrylic acid.
9. A defect-rich carbon material produced by the production method according to any one of claims 1 to 8.
10. Use of the defect-rich carbon material of claim 9 or the defect-rich carbon material produced by the production method of any one of claims 1 to 8 as an electrocatalyst for fuel cells.
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