CN110947374A - Hydroxyl metal oxide nano catalyst and preparation method thereof - Google Patents
Hydroxyl metal oxide nano catalyst and preparation method thereof Download PDFInfo
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- CN110947374A CN110947374A CN201911294089.6A CN201911294089A CN110947374A CN 110947374 A CN110947374 A CN 110947374A CN 201911294089 A CN201911294089 A CN 201911294089A CN 110947374 A CN110947374 A CN 110947374A
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- Prior art keywords
- acid
- metal oxide
- deionized water
- acetate
- sulfate
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- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 47
- -1 Hydroxyl metal oxide Chemical class 0.000 title claims abstract description 45
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000008367 deionised water Substances 0.000 claims abstract description 42
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 42
- 239000000243 solution Substances 0.000 claims abstract description 38
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000376 reactant Substances 0.000 claims abstract description 29
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004202 carbamide Substances 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000012670 alkaline solution Substances 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 239000007800 oxidant agent Substances 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- 238000004140 cleaning Methods 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 238000003760 magnetic stirring Methods 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 229910052799 carbon Inorganic materials 0.000 claims description 36
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims description 15
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 8
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 7
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 7
- 239000006260 foam Substances 0.000 claims description 7
- 239000012286 potassium permanganate Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 5
- 229940044175 cobalt sulfate Drugs 0.000 claims description 5
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 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
- 239000010936 titanium Substances 0.000 claims description 4
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 claims description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 claims description 2
- MFWFDRBPQDXFRC-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;vanadium Chemical compound [V].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MFWFDRBPQDXFRC-LNTINUHCSA-N 0.000 claims description 2
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride 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
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-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
- 229910021550 Vanadium Chloride Inorganic materials 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 2
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 claims description 2
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 2
- 229940097267 cobaltous chloride Drugs 0.000 claims description 2
- 229940045032 cobaltous nitrate Drugs 0.000 claims description 2
- 239000011889 copper foil Substances 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011888 foil Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Inorganic materials Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 claims description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- VLOPEOIIELCUML-UHFFFAOYSA-L vanadium(2+);sulfate Chemical compound [V+2].[O-]S([O-])(=O)=O VLOPEOIIELCUML-UHFFFAOYSA-L 0.000 claims description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims 2
- 230000007547 defect Effects 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000007809 chemical reaction catalyst Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 13
- 238000001914 filtration Methods 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 229910018916 CoOOH Inorganic materials 0.000 description 7
- 238000005054 agglomeration Methods 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- 229910002588 FeOOH Inorganic materials 0.000 description 3
- 229910003174 MnOOH Inorganic materials 0.000 description 3
- 229910002640 NiOOH Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000001844 chromium Chemical class 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 150000003681 vanadium Chemical class 0.000 description 2
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 description 1
- RTBHLGSMKCPLCQ-UHFFFAOYSA-N [Mn].OOO Chemical compound [Mn].OOO RTBHLGSMKCPLCQ-UHFFFAOYSA-N 0.000 description 1
- OSOVKCSKTAIGGF-UHFFFAOYSA-N [Ni].OOO Chemical compound [Ni].OOO OSOVKCSKTAIGGF-UHFFFAOYSA-N 0.000 description 1
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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Abstract
The invention discloses a hydroxyl metal oxide nano catalyst and a preparation method thereof, wherein the preparation method comprises the following steps: 1) ultrasonically cleaning a conductive substrate by using acid, ethanol, acetone and deionized water in sequence to obtain a conductive substrate with a clean surface and rich defects; 2) adding metal salt and urea into deionized water and an organic solvent for dissolving, transferring the solution into a liner of a reaction kettle, then adding a conductive substrate with a clean surface and rich defects, carrying out hydrothermal reaction under a certain condition, washing and drying a product to obtain a reactant 1; 3) adding the reactant 1 into deionized water and an alkaline solution, then adding an oxidant, carrying out magnetic stirring reaction under the oil bath condition, washing and drying a product to obtain the hydroxyl metal oxide nano catalyst. The invention solves the problems of complex synthesis, low activity and poor stability of the oxygen evolution reaction catalyst prepared by the prior art.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a hydroxyl metal oxide nano catalyst and a preparation method thereof.
Background
Hydrogen is a renewable energy source with high energy density, cleanness and no pollution. Proton Exchange Membrane Water Electrolysers (PEMWE) are widely considered as a very promising means of converting intermittent solar or wind energy into sustainable hydrogen energy due to their high energy efficiency, high productivity and high purity of hydrogen gas, compared to conventional steam reforming of methane. Water electrolysis involves two half-reactions: hydrogen Evolution Reaction (HER) and Oxygen Evolution Reaction (OER). Unfortunately, OER on the anode side is still subject to slow reaction kinetics compared to the minimal energy loss of the HER on the cathode side, and becomes a major bottleneck for practical application of PEMWE, and therefore, an electrocatalyst capable of efficiently evolving oxygen needs to be designed to improve the efficiency of PEMWE. Heretofore, noble metal oxide catalysts (e.g., IrO)2And RuO2) Considered the most advanced OER catalysts, the low reserves of Ir and Ru are the major limitations for their widespread use. Therefore, the search for alternatives to noble metal compound catalysts has attracted considerable attention. Non-noble metals (Fe, Co, Ni, Mn, Cu, etc.) and their compounds have been widely reported as OER catalysts with application prospects, but still require very large overpotentials (at 10mA cm)-2At current density>300mV) was used to drive the reaction. Meanwhile, the problems of low reaction efficiency, poor stability and the like exist in the OER reaction catalyzed by using a non-noble metal catalyst instead of noble metal. Therefore, the development of non-noble metal catalysts with high activity and high stability is urgently required to solve the above problems, but it remains a great challenge.
In recent years, transition metal oxyhydroxides (MOOH, M ═ Co, Fe, Ni, and the like) have been confirmed to have activity to catalyze Oxygen Evolution Reaction (OER) and have been widely noticed and studied. However, the transition metal oxyhydroxide catalysts of the type reported in the literature have the following problems: 1) the synthesis method is complicated; 2) the conductivity is low; 3) catalyst particles are easy to agglomerate in the reaction process, so that the catalytic activity and the stability are reduced. Therefore, there is still a lot of work to be done to address the above problems.
Disclosure of Invention
In view of the above, an object of the present invention is to prepare a metal oxide hydroxide nano-catalyst with high OER activity.
The invention also aims to provide a preparation method of the hydroxyl metal oxide nano-catalyst.
In order to achieve the purpose, the invention adopts the following technical scheme.
The preparation method of the hydroxyl metal oxide nano catalyst is characterized by comprising the following steps of:
1) ultrasonically cleaning a conductive substrate by using acid, ethanol, acetone and deionized water in sequence to obtain a conductive substrate with a clean surface;
2) adding metal salt and urea into deionized water and an organic solvent for dissolving, transferring the solution into a liner of a reaction kettle, then adding a conductive substrate with a clean surface, carrying out hydrothermal reaction under a certain condition, washing and drying a product to obtain a reactant 1;
3) adding the reactant 1 into deionized water and an alkaline solution, then adding an oxidant, carrying out magnetic stirring reaction under the condition of oil bath, washing and drying a product to obtain the hydroxyl metal oxide nano catalyst.
Preferably, in step 1), the acid is selected from one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, hypochlorous acid and acetic acid, formic acid, oxalic acid.
Preferably, in step 1), the conductive substrate is one of carbon paper, carbon cloth, carbon nanotube, titanium felt, titanium mesh, cobalt foam, iron foam, nickel foam, copper foil, aluminum foil, graphene, graphite alkyne and MXene.
Preferably, in step 2), the transition metal salt is selected from one or two of iron salt, cobalt salt, nickel salt, vanadium salt, manganese salt or chromium salt; the ferric salt is selected from one of ferric chloride, ferrous chloride, ferric sulfate, ferrous sulfate, ferric nitrate, ferrous nitrate, ferric acetate, ferrous acetate and ferric acetylacetonate; the cobalt salt is selected from one of cobalt chloride, cobaltous chloride, cobalt sulfate, cobaltous sulfate, cobalt nitrate, cobaltous nitrate, cobalt acetate, cobaltous acetate and cobalt acetylacetonate; the nickel salt is selected from one of nickel chloride, nickel sulfate, nickel nitrate, nickel acetate and nickel acetylacetonate; the vanadium salt is selected from one of vanadium sulfate, vanadium chloride, vanadium acetylacetonate, vanadyl acetylacetonate and ammonium metavanadate; the manganese salt is selected from one of manganese sulfate, manganese chloride, manganese nitrate, manganese acetate and potassium permanganate; the chromium salt is selected from one of chromium chloride, chromium sulfate, chromium nitrate, chromium acetate, ammonium dichromate and potassium dichromate.
Preferably, in step 2), the organic solvent is one or two of methanol, ethanol, ethylene glycol, isopropanol, acetone, N-methylpyrrolidone and N-hexane.
Preferably, in step 3), the alkaline solution is one or two of sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia water, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium acetate, potassium acetate and sodium sulfide.
Preferably, in step 3), the oxidant is one or two of ozone, chlorine, bromine water, iodine, potassium permanganate, potassium dichromate, potassium chlorate, concentrated sulfuric acid, concentrated nitric acid, manganese dioxide and hydrogen peroxide.
Preferably, in the step 2), the hydrothermal reaction temperature is 30-200 ℃, more preferably 50-180 ℃, most preferably 80-120 ℃, the reaction time is 1-48 hours, more preferably 3-36 hours, and most preferably 5-24 hours.
Preferably, in the step 3), the oil bath reaction temperature is 30-200 ℃, more preferably 30-150 ℃, most preferably 40-100 ℃, the reaction time is 1-48 hours, more preferably 3-36 hours, and most preferably 5-24 hours.
The invention also provides a hydroxyl metal oxide nano catalyst, which comprises the hydroxyl metal oxide nano catalyst obtained by the preparation method.
Compared with the existing method for preparing the hydroxyl metal oxide, the method introduces the conductive substrate with high conductive property and excellent mechanical stability to stably and uniformly disperse the hydroxyl metal oxide, so that the hydroxyl metal oxide nano catalyst with the three-way catalyst active site is designed and constructed, and the three-dimensional nano catalyst shows self-support and high conductive performance. Therefore, the hydroxyl metal oxide nano-catalyst of the invention shows excellent catalytic activity and good stability for OER.
The hydroxyl metal oxide nano catalyst obtained by the specific preparation method of the invention has high catalytic activity on OER, and solves the problems of complex synthesis method, low conductivity and low OER activity and stability caused by agglomeration easily in the traditional hydroxyl metal oxide synthesis method. The preparation method of the hydroxyl metal oxide nano catalyst has the advantages of simple process, low cost and easy scale production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
Fig. 1 is a scanning electron microscope image of the surface-cleaned carbon paper prepared in example 1 of the present invention.
FIG. 2 is a scanning electron micrograph of reactant 1 prepared in example 1 of the present invention.
FIG. 3 is a scanning electron micrograph of CoOOH/CP prepared according to example 1 of the present invention.
FIG. 4 is a scanning electron micrograph of FeOOH/CP prepared in example 5 of the present invention.
FIG. 5 is a scanning electron micrograph of NiOOH/MXene prepared according to example 7 of the present invention.
FIG. 6 is a scanning electron micrograph of VOOH/MXene prepared according to EXAMPLE 8 of the present invention.
FIG. 7 is a scanning electron micrograph of MnOOH/CP prepared according to example 9 of the present invention.
Detailed Description
The invention provides a hydroxyl metal oxide nano catalyst and a preparation method thereof, which can solve the problems of complex synthesis method, low activity and poor stability of an OER catalyst prepared by the prior art.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The raw materials used in the following examples are all commercially available or self-made.
Example 1
This example provides a first hydroxy metal oxide nanocatalyst, which is prepared by the following steps:
1) the carbon paper is sequentially ultrasonically cleaned by nitric acid, ethanol, acetone and deionized water to obtain the carbon paper with a clean surface and rich defects, and attachment sites are added for the growth of the subsequent hydrothermal reaction.
2) Dissolving cobalt sulfate and urea in deionized water and ethylene glycol to obtain a solution a, adding the carbon paper obtained by the treatment in the step 1) into the solution a, carrying out hydrothermal reaction at 100 ℃ for 5 hours, and sequentially filtering and drying the product to obtain a reactant 1.
3) Adding the reactant 1 obtained by the treatment in the step 2) into deionized water and a sodium hydroxide solution, then adding potassium permanganate, and carrying out oil bath at 45 ℃ for 18 hours to obtain the Carbon Paper (CP) supported cobalt oxyhydroxide nano catalyst (CoOOH/CP).
From the change from fig. 1 to fig. 3, it can be seen that: after the carbon paper is introduced, the hydroxyl metal oxide can uniformly grow on the carbon paper; and after the hydroxyl metal oxide uniformly grown on the carbon paper is subjected to a specific oxidation treatment process, a three-dimensional self-supporting nano catalyst with rich catalytic active sites can be designed and constructed, almost no agglomeration exists, and the catalytic activity is excellent.
Example 2
This example provides a second hydroxy metal oxide nanocatalyst, which is prepared by the following steps:
1) the carbon paper is sequentially ultrasonically cleaned by nitric acid, ethanol, acetone and deionized water to obtain the carbon paper with a clean surface and rich defects, and attachment sites are added for the subsequent hydrothermal reaction growth.
2) Dissolving cobalt nitrate and urea in deionized water and ethylene glycol to obtain a solution a, then adding the carbon paper obtained by the treatment in the step 1) into the solution a, carrying out hydrothermal reaction at 80 ℃ for 10 hours, and sequentially filtering and drying the product to obtain a reactant 1.
3) Adding the reactant 1 obtained by the treatment in the step 2) into deionized water and a sodium hydroxide solution, then adding potassium permanganate, and carrying out oil bath at 40 ℃ for 24 hours to obtain the Carbon Paper (CP) supported cobalt oxyhydroxide nano catalyst (CoOOH/CP).
Example 3
This example provides a third hydroxy metal oxide nanocatalyst prepared as follows:
1) the carbon paper is sequentially ultrasonically cleaned by nitric acid, ethanol, acetone and deionized water to obtain the carbon paper with a clean surface and rich defects, and attachment sites are added for the subsequent hydrothermal reaction growth.
2) Dissolving cobalt chloride and urea in deionized water and N-methylpyrrolidone to obtain a solution a, adding the carbon paper obtained by the treatment in the step 1 into the solution a, carrying out hydrothermal reaction at 120 ℃ for 8 hours, and sequentially filtering and drying the product to obtain a reactant 1.
3) Adding the reactant 1 obtained by the treatment in the step 2) into deionized water and a sodium hydroxide solution, then adding potassium permanganate, and carrying out oil bath at 100 ℃ for 5 hours to obtain the Carbon Paper (CP) supported cobalt oxyhydroxide nano catalyst (CoOOH/CP).
Example 4
This example provides a fourth hydroxy metal oxide nanocatalyst, which is prepared by the following steps:
1) the carbon paper is sequentially ultrasonically cleaned by nitric acid, ethanol, acetone and deionized water to obtain the carbon paper with a clean surface and rich defects, and attachment sites are added for the subsequent hydrothermal reaction growth.
2) Dissolving cobalt acetate and urea in deionized water and N-methylpyrrolidone to obtain a solution a, adding the carbon paper obtained by the treatment in the step 1 into the solution a, carrying out hydrothermal reaction at 200 ℃ for 1 hour, and sequentially filtering and drying the product to obtain a reactant 1.
3) Adding the reactant 1 obtained by the treatment in the step 2) into deionized water and a sodium hydroxide solution, then adding hydrogen peroxide, and carrying out oil bath at 200 ℃ for 1 hour to obtain the Carbon Paper (CP) supported cobalt oxyhydroxide nano catalyst (CoOOH/CP).
Example 5
This example provides a fifth hydroxy metal oxide nanocatalyst, which is prepared by the following steps:
1) the carbon paper is sequentially ultrasonically cleaned by nitric acid, ethanol, acetone and deionized water to obtain the carbon paper with a clean surface and rich defects, and attachment sites are added for the subsequent hydrothermal reaction growth.
2) And (2) dissolving ferric sulfate and urea in deionized water and N-methylpyrrolidone to obtain a solution a, adding the carbon paper obtained by the treatment in the step (1) into the solution a, carrying out hydrothermal reaction at 100 ℃ for 5 hours, and sequentially filtering and drying the product to obtain a reactant 1.
3) Adding the reactant 1 obtained by the treatment in the step 2) into deionized water and a sodium hydroxide solution, then adding hydrogen peroxide, and carrying out oil bath at 60 ℃ for 24 hours to obtain the Carbon Paper (CP) supported iron oxyhydroxide nano catalyst (FeOOH/CP).
As can be seen from fig. 4: the FeOOH/CP prepared by the embodiment has almost no agglomeration, and the three-dimensional self-supporting nano-catalyst with rich catalytic active sites is constructed, so that the catalytic activity is excellent.
Example 6
This example provides a sixth hydroxy metal oxide nanocatalyst, which is prepared by the following steps:
1) the foamed nickel is sequentially ultrasonically cleaned by nitric acid, ethanol, acetone and deionized water to obtain the foamed nickel with a clean surface and rich defects, and attachment sites are added for the growth of the subsequent hydrothermal reaction.
2) Dissolving cobalt sulfate and urea in deionized water and N-methylpyrrolidone to obtain a solution a, adding the foamed nickel obtained by the step 1 into the solution a, carrying out hydrothermal reaction at 30 ℃ for 48 hours, and sequentially filtering and drying the product to obtain a reactant 1.
3) Adding the reactant 1 obtained by the treatment in the step 2) into deionized water and a sodium hydroxide solution, then adding hydrogen peroxide, and carrying out oil bath at 30 ℃ for 48 hours to obtain the foam Nickel (NF) supported cobalt oxyhydroxide nano catalyst (CoOOH/NF).
Example 7
This example provides a seventh hydroxy metal oxide nanocatalyst, which is prepared by the following steps:
1) the MXene is sequentially ultrasonically cleaned by nitric acid, ethanol, acetone and deionized water to obtain the MXene with a clean surface and rich defects, and attachment sites are added for the growth of the subsequent hydrothermal reaction.
2) Dissolving nickel sulfate and urea in deionized water and N-methylpyrrolidone to obtain a solution a, adding MXene obtained by the treatment in the step 1 into the solution a, carrying out hydrothermal reaction at 180 ℃ for 3 hours, and sequentially filtering and drying the product to obtain a reactant 1.
3) Adding the reactant 1 obtained by the treatment in the step 2) into deionized water and a sodium hydroxide solution, then adding hydrogen peroxide, and carrying out oil bath at 150 ℃ for 3 hours to obtain the MXene supported nickel oxyhydroxide nano catalyst (NiOOH/MXene).
As can be seen from fig. 5: the NiOOH/MXene prepared by the embodiment is almost free of agglomeration, the three-dimensional self-supporting nano-catalyst with rich catalytic active sites is constructed, and the catalytic activity is excellent.
Example 8
This example provides an eighth hydroxy metal oxide nanocatalyst, which is prepared by the following steps:
1) the MXene is sequentially ultrasonically cleaned by nitric acid, ethanol, acetone and deionized water to obtain the MXene with a clean surface and rich defects, and attachment sites are added for the growth of the subsequent hydrothermal reaction.
2) Dissolving ammonium metavanadate and urea in deionized water and N-methylpyrrolidone to obtain a solution a, adding MXene obtained by the treatment in the step 1 into the solution a, carrying out hydrothermal reaction at 160 ℃ for 8 hours, and sequentially filtering and drying the product to obtain a reactant 1.
3) Adding the reactant 1 obtained by the treatment in the step 2) into deionized water and a sodium hydroxide solution, then adding hydrogen peroxide, and carrying out oil bath at 50 ℃ for 36 hours to obtain the MXene supported hydroxyl vanadium oxide nano catalyst (VOOH/MXene).
As can be seen from fig. 6: the VOOH/MXene prepared by the embodiment is almost free of agglomeration, the three-dimensional self-supporting nano-catalyst with rich catalytic active sites is constructed, and the catalytic activity is excellent.
Example 9
This example provides a ninth hydroxy metal oxide nanocatalyst, which is prepared by the following steps:
1) the carbon paper is sequentially ultrasonically cleaned by nitric acid, ethanol, acetone and deionized water to obtain the carbon paper with a clean surface and rich defects, and attachment sites are added for the subsequent hydrothermal reaction growth.
2) Dissolving manganese acetate and urea in deionized water and N-methyl pyrrolidone to obtain a solution a, adding the carbon paper obtained by the treatment in the step 1 into the solution a, carrying out hydrothermal reaction at 140 ℃ for 24 hours, and sequentially filtering and drying the product to obtain a reactant 1.
3) Adding the reactant 1 obtained by the treatment in the step 2) into deionized water and a sodium hydroxide solution, then adding hydrogen peroxide, and carrying out oil bath at 60 ℃ for 24 hours to obtain the Carbon Paper (CP) supported manganese oxyhydroxide nano catalyst (MnOOH/CP).
As can be seen from fig. 7: the MnOOH/CP prepared by the embodiment has almost no agglomeration, and the three-dimensional self-supporting nano-catalyst with abundant catalytic active sites is constructed, so that the catalytic activity is excellent.
Example 10
This example provides a tenth hydroxy metal oxide nanocatalyst, which is prepared by the following steps:
1) and ultrasonically cleaning the titanium mesh by using nitric acid, ethanol, acetone and deionized water in sequence to obtain the titanium mesh with a clean surface and rich defects, so that attachment sites are increased for the growth of the subsequent hydrothermal reaction.
2) And (2) dissolving ammonium dichromate and urea in deionized water and N-methylpyrrolidone to obtain a solution a, then adding the titanium mesh obtained by the treatment in the step (1) into the solution a, carrying out hydrothermal reaction at 50 ℃ for 48 hours, and sequentially filtering and drying the product to obtain a reactant 1.
3) Adding the reactant 1 obtained by the treatment in the step 2) into deionized water and a sodium hydroxide solution, then adding hydrogen peroxide, and carrying out oil bath at 150 ℃ for 12 hours to obtain the titanium mesh (Ti) supported cobalt oxyhydroxide nano catalyst (CrOOH/Ti).
Comparative example 1
This example provides a comparative example, which was prepared as follows:
1) the carbon paper is sequentially ultrasonically cleaned by nitric acid, ethanol, acetone and deionized water to obtain the carbon paper with a clean surface and rich defects, and attachment sites are added for the subsequent hydrothermal reaction growth.
2) Dissolving cobalt sulfate and urea in deionized water and ethylene glycol to obtain a solution a, adding the carbon paper obtained by the treatment in the step 1 into the solution a, carrying out hydrothermal reaction at 100 ℃ for 5 hours, and sequentially filtering and drying the product to obtain a reactant 1.
3) Adding the reactant 1 obtained by the treatment in the step 2) into deionized water and sodium hydroxide solution, and then adding concentrated H2SO4Oil bath was carried out at 45 ℃ for 18 hours.
The Carbon Paper (CP) supported cobalt oxyhydroxide nanocatalyst (CoOOH/CP) could not be obtained with the method of the comparative example.
It will be appreciated by those skilled in the art from the foregoing description of construction and principles that the invention is not limited to the specific embodiments described above, and that modifications and substitutions based on the teachings of the art may be made without departing from the scope of the invention as defined by the appended claims and their equivalents. The details not described in the detailed description are prior art or common general knowledge.
Claims (10)
1. The preparation method of the hydroxyl metal oxide nano catalyst is characterized by comprising the following steps of:
1) ultrasonically cleaning a conductive substrate by using acid, ethanol, acetone and deionized water in sequence to obtain a conductive substrate with a clean surface;
2) adding metal salt and urea into deionized water and an organic solvent for dissolving, transferring the solution into a liner of a reaction kettle, then adding a conductive substrate with a clean surface, carrying out hydrothermal reaction under a certain condition, washing and drying a product to obtain a reactant 1;
3) adding the reactant 1 into deionized water and an alkaline solution, then adding an oxidant, carrying out magnetic stirring reaction under the condition of oil bath, washing and drying a product to obtain the hydroxyl metal oxide nano catalyst.
2. The method according to claim 1, wherein in step 1), the acid is one selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, hypochlorous acid, acetic acid, formic acid, and oxalic acid.
3. The method according to claim 1, wherein in step 1), the conductive substrate is one of carbon paper, carbon cloth, carbon nanotube, titanium felt, titanium mesh, cobalt foam, iron foam, nickel foam, copper foil, aluminum foil, graphene, graphite alkyne, and MXene.
4. The method according to claim 1, wherein in step 2), the metal salt is selected from one or two of ferric chloride, ferrous chloride, ferric sulfate, ferrous sulfate, ferric nitrate, ferrous nitrate, ferric acetate, ferrous acetate, ferric acetylacetonate, cobalt chloride, cobaltous chloride, cobalt sulfate, cobaltous sulfate, cobalt nitrate, cobaltous nitrate, cobalt acetate, cobalt acetylacetonate, nickel chloride, nickel sulfate, nickel nitrate, nickel acetate, nickel acetylacetonate, vanadium sulfate, vanadium chloride, vanadium acetylacetonate, vanadyl acetylacetonate, ammonium metavanadate, manganese sulfate, manganese chloride, manganese nitrate, manganese acetate, potassium permanganate, chromium chloride, chromium sulfate, chromium nitrate, chromium acetate, ammonium dichromate, and potassium dichromate.
5. The method according to claim 1, wherein in step 2), the organic solvent is one or two selected from methanol, ethanol, ethylene glycol, isopropanol, diethyl ether, acetone, N-methylpyrrolidone, ethyl acetate, dichloromethane, N-hexane, and chloroform.
6. The method according to claim 1, wherein in the step 2), the hydrothermal reaction temperature is 30 to 200 ℃ and the reaction time is 1 to 48 hours.
7. The method according to claim 1, wherein in step 3), the alkaline solution is one or two of sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia water, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium acetate, potassium acetate, and sodium sulfide.
8. The preparation method according to claim 1, wherein in step 3), the oxidant is one or two of ozone, chlorine, bromine water, iodine, potassium permanganate, potassium dichromate, potassium chlorate, concentrated sulfuric acid, concentrated nitric acid, manganese dioxide and hydrogen peroxide.
9. The production method according to claim 1, wherein in the step 3), the oil bath condition is performed at a reaction temperature of 30 to 200 ℃ for 1 to 48 hours.
10. A hydroxy metal oxide nanocatalyst, comprising the hydroxy metal oxide nanocatalyst obtained by the preparation method according to any one of claims 1 to 9.
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