CN114892196B - Hierarchical porous material and preparation method and application thereof - Google Patents
Hierarchical porous material and preparation method and application thereof Download PDFInfo
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- CN114892196B CN114892196B CN202210668347.8A CN202210668347A CN114892196B CN 114892196 B CN114892196 B CN 114892196B CN 202210668347 A CN202210668347 A CN 202210668347A CN 114892196 B CN114892196 B CN 114892196B
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- 239000011148 porous material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 90
- 238000002156 mixing Methods 0.000 claims abstract description 71
- 239000002149 hierarchical pore Substances 0.000 claims abstract description 68
- 239000002184 metal Chemical class 0.000 claims abstract description 55
- 229910052751 metal Inorganic materials 0.000 claims abstract description 55
- 239000002798 polar solvent Substances 0.000 claims abstract description 50
- 239000002243 precursor Substances 0.000 claims abstract description 47
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000011159 matrix material Substances 0.000 claims abstract description 45
- 150000003839 salts Chemical class 0.000 claims abstract description 43
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000002253 acid Substances 0.000 claims abstract description 27
- 238000002386 leaching Methods 0.000 claims abstract description 27
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 23
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 23
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 18
- 238000011065 in-situ storage Methods 0.000 claims abstract description 13
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 9
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 9
- 239000003607 modifier Substances 0.000 claims abstract description 9
- 239000003575 carbonaceous material Substances 0.000 claims description 33
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 16
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 15
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 14
- 239000001095 magnesium carbonate Substances 0.000 claims description 14
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 14
- 150000001868 cobalt Chemical class 0.000 claims description 12
- 150000001879 copper Chemical class 0.000 claims description 12
- 150000002696 manganese Chemical class 0.000 claims description 12
- 150000002815 nickel Chemical class 0.000 claims description 12
- 238000006722 reduction reaction Methods 0.000 claims description 12
- 150000003303 ruthenium Chemical class 0.000 claims description 12
- 239000013110 organic ligand Substances 0.000 claims description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 8
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 6
- 150000003751 zinc Chemical class 0.000 claims description 6
- 229910021536 Zeolite Inorganic materials 0.000 claims description 5
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 26
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 20
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 20
- 239000003054 catalyst Substances 0.000 abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 159
- 239000011259 mixed solution Substances 0.000 description 107
- 238000003756 stirring Methods 0.000 description 73
- 239000002244 precipitate Substances 0.000 description 65
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 47
- 238000010438 heat treatment Methods 0.000 description 41
- 238000001035 drying Methods 0.000 description 34
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 28
- 239000000126 substance Substances 0.000 description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 26
- 239000000047 product Substances 0.000 description 24
- 239000000243 solution Substances 0.000 description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- 238000010668 complexation reaction Methods 0.000 description 17
- 238000000227 grinding Methods 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 17
- 238000001816 cooling Methods 0.000 description 15
- 238000001914 filtration Methods 0.000 description 15
- 238000010992 reflux Methods 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 229910001873 dinitrogen Inorganic materials 0.000 description 13
- 238000011068 loading method Methods 0.000 description 13
- 229910052759 nickel Inorganic materials 0.000 description 13
- 239000003921 oil Substances 0.000 description 13
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 13
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 13
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 13
- 239000000843 powder Substances 0.000 description 13
- 238000009210 therapy by ultrasound Methods 0.000 description 13
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 12
- HZUJFPFEXQTAEL-UHFFFAOYSA-N azanylidynenickel Chemical compound [N].[Ni] HZUJFPFEXQTAEL-UHFFFAOYSA-N 0.000 description 12
- 238000004090 dissolution Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 10
- 150000002505 iron Chemical class 0.000 description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 8
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 5
- 239000012445 acidic reagent Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- XIELUSWGOAVQLB-UHFFFAOYSA-N [N].[Ag] Chemical compound [N].[Ag] XIELUSWGOAVQLB-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- 230000000536 complexating effect Effects 0.000 description 4
- 229910000365 copper sulfate Inorganic materials 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 229910001961 silver nitrate Inorganic materials 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- FTXJFNVGIDRLEM-UHFFFAOYSA-N copper;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O FTXJFNVGIDRLEM-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 3
- YMKHJSXMVZVZNU-UHFFFAOYSA-N manganese(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YMKHJSXMVZVZNU-UHFFFAOYSA-N 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 3
- 150000003460 sulfonic acids Chemical class 0.000 description 3
- OAVRWNUUOUXDFH-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;manganese(2+) Chemical compound [Mn+2].[Mn+2].[Mn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O OAVRWNUUOUXDFH-UHFFFAOYSA-H 0.000 description 2
- UPPLJLAHMKABPR-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;nickel(2+) Chemical compound [Ni+2].[Ni+2].[Ni+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O UPPLJLAHMKABPR-UHFFFAOYSA-H 0.000 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 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- DKKCQDROTDCQOR-UHFFFAOYSA-L Ferrous lactate Chemical compound [Fe+2].CC(O)C([O-])=O.CC(O)C([O-])=O DKKCQDROTDCQOR-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- CMPNPRUFRJFQIB-UHFFFAOYSA-N [N].[Cu] Chemical compound [N].[Cu] CMPNPRUFRJFQIB-UHFFFAOYSA-N 0.000 description 2
- BTSUQRSYTQIQCM-UHFFFAOYSA-N [N].[Ru] Chemical compound [N].[Ru] BTSUQRSYTQIQCM-UHFFFAOYSA-N 0.000 description 2
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- FRHBOQMZUOWXQL-UHFFFAOYSA-L ammonium ferric citrate Chemical compound [NH4+].[Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FRHBOQMZUOWXQL-UHFFFAOYSA-L 0.000 description 2
- 239000003011 anion exchange membrane Substances 0.000 description 2
- YDVGDXLABZAVCP-UHFFFAOYSA-N azanylidynecobalt Chemical compound [N].[Co] YDVGDXLABZAVCP-UHFFFAOYSA-N 0.000 description 2
- RBVYPNHAAJQXIW-UHFFFAOYSA-N azanylidynemanganese Chemical compound [N].[Mn] RBVYPNHAAJQXIW-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- SCNCIXKLOBXDQB-UHFFFAOYSA-K cobalt(3+);2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Co+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O SCNCIXKLOBXDQB-UHFFFAOYSA-K 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- YHGGQZOFJGJAMR-UHFFFAOYSA-N cyclopenta-1,3-diene ruthenium Chemical compound C1=CC=CC1.C1=CC=CC1.[Ru] YHGGQZOFJGJAMR-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229960004642 ferric ammonium citrate Drugs 0.000 description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- 239000011640 ferrous citrate Substances 0.000 description 2
- 235000019850 ferrous citrate Nutrition 0.000 description 2
- 239000004225 ferrous lactate Substances 0.000 description 2
- 235000013925 ferrous lactate Nutrition 0.000 description 2
- 229940037907 ferrous lactate Drugs 0.000 description 2
- 229960001781 ferrous sulfate Drugs 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000004313 iron ammonium citrate Substances 0.000 description 2
- 235000000011 iron ammonium citrate Nutrition 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 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 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- APVZWAOKZPNDNR-UHFFFAOYSA-L iron(ii) citrate Chemical compound [Fe+2].OC(=O)CC(O)(C([O-])=O)CC([O-])=O APVZWAOKZPNDNR-UHFFFAOYSA-L 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- 239000011564 manganese citrate Substances 0.000 description 2
- 235000014872 manganese citrate Nutrition 0.000 description 2
- 229940097206 manganese citrate Drugs 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229940022663 acetate Drugs 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- YYXHRUSBEPGBCD-UHFFFAOYSA-N azanylidyneiron Chemical compound [N].[Fe] YYXHRUSBEPGBCD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001350 scanning transmission electron microscopy Methods 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004246 zinc acetate Substances 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
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/23—Carbon monoxide or syngas
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/03—Acyclic or carbocyclic hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
- C25B3/26—Reduction of carbon dioxide
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of carbon dioxide reduction, and particularly relates to a hierarchical porous material, a preparation method and application thereof. The invention provides a preparation method of a hierarchical pore material, which comprises the following steps: mixing a template agent, a surface modifier and a polar solvent to obtain a matrix material; growing metal organic compounds on the surface of the matrix material in situ to obtain a precursor material; sequentially roasting and acid leaching the precursor material to obtain the hierarchical pore material; the template agent has a loose porous structure; the template agent comprises one or more of metal oxide, metal salt and silicon oxide. When the hierarchical porous material obtained by the preparation method provided by the invention is used as a catalyst for preparing carbon monoxide by electrochemical reduction of carbon dioxide, the reaction kinetics in the carbon dioxide conversion process can be further improved, and the Faraday efficiency and the current distribution density of the carbon monoxide are improved.
Description
Technical Field
The invention belongs to the technical field of carbon dioxide reduction, and particularly relates to a hierarchical porous material, a preparation method and application thereof.
Background
The combustion of fossil fuels causes excessive emissions of carbon dioxide, accelerating global warming, resulting in sea level elevation and a series of extreme weather occurrences. Therefore, conversion of carbon dioxide to valuable carbon products is imperative.
Among the existing carbon dioxide conversion technologies, the carbon dioxide electrochemical reduction technology has the advantages of mild reaction conditions, easy control of reaction and easy modularization. The product of electrochemical reduction of carbon dioxide mainly comprises carbon monoxide, methane, ethylene, formate, acetate, methanol or ethanol, wherein the carbon monoxide has the advantages of high selectivity and easy separation from electrolyte, and can be used as a chemical raw material to directly participate in industrial synthesis.
The catalyst for preparing carbon monoxide by electrochemical reduction of carbon dioxide mainly comprises a silver alloy catalyst, a carbon nano tube supported metal composite catalyst and the like, but the activity of the existing catalyst is low, so that the defects of low pulling efficiency and low current distribution density of a carbon monoxide method in the electrochemical reduction process of carbon dioxide are caused.
Disclosure of Invention
The invention aims to provide a hierarchical pore material, a preparation method and application thereof, and the hierarchical pore material prepared by the method can be used as a catalyst for preparing carbon monoxide by electrochemical reduction of carbon dioxide, so that the Faraday efficiency and the current dividing density of the carbon monoxide can be improved.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a hierarchical pore material, which comprises the following steps:
mixing a template agent, a surface modifier and a polar solvent to obtain a matrix material;
growing metal organic compounds on the surface of the matrix material in situ to obtain a precursor material;
sequentially roasting and acid leaching the precursor material to obtain the hierarchical pore material;
the template agent has a loose porous structure;
the template agent comprises one or more of metal oxide, metal salt and silicon oxide.
Preferably, the metal oxide comprises magnesium oxide and/or zinc oxide; the metal salt comprises basic magnesium carbonate; the oxide of silicon comprises silicon dioxide.
Preferably, the metal organic compound comprises a zeolite imidazole framework or a metal organic complex.
Preferably, when the metal organic compound is a zeolitic imidazolate framework, the in situ growth comprises the steps of: mixing the matrix material, the first soluble metal salt, the second soluble metal salt, the 2-methylimidazole and the polar solvent, and carrying out a meridian-complex reaction to obtain the precursor material;
The first soluble metal salt is a soluble zinc salt;
the second soluble metal salt comprises one or more of soluble nickel salt, soluble ferric salt, soluble cobalt salt, soluble copper salt, soluble manganese salt, soluble ruthenium salt and soluble silver salt.
Preferably, when the metal organic compound is a metal organic complex, the in situ growth comprises the steps of:
mixing a matrix material, soluble metal salt, an organic ligand and a polar solvent, and carrying out meridian combination reaction to obtain the precursor material;
the soluble metal salt comprises one or more of soluble nickel salt, soluble ferric salt, soluble cobalt salt, soluble copper salt, soluble manganese salt, soluble ruthenium salt and soluble silver salt;
the organic ligand comprises one or more of phenanthroline, formamide, melamine and polyaniline.
Preferably, the roasting temperature is 600-1200 ℃, and the heat preservation time is 0.5-10 h.
Preferably, the template is replaced with polystyrene;
when the template agent is polystyrene, the preparation method of the hierarchical pore material does not comprise acid leaching treatment.
The invention also provides the hierarchical pore material prepared by the preparation method of the technical scheme, and the hierarchical pore material is a metal doped hierarchical pore carbon material.
Preferably, the metal comprises one or more of nickel, iron, cobalt, copper, manganese, ruthenium and silver;
the mass percentage of the metal is 0.5-15.0%.
The invention also provides application of the hierarchical porous material in catalyzing carbon dioxide reduction reaction.
The invention provides a preparation method of a hierarchical pore material, which comprises the following steps: mixing a template agent, a surface modifier and a polar solvent to obtain a matrix material; growing metal organic compounds on the surface of the matrix material in situ to obtain a precursor material; sequentially roasting and acid leaching the precursor material to obtain the hierarchical pore material; the template agent has a loose porous structure; the template agent comprises one or more of metal oxide, metal salt and silicon oxide. According to the invention, the metal organic compound grows on the surface of the template agent with a loose porous structure in situ, after roasting and acid leaching treatment, the metal organic compound can form a multistage pore structure similar to the shape of the template agent, and meanwhile, after roasting and acid leaching treatment, the loose porous structure of the template agent can be transferred to a carbon material, so that a metal-doped carbon material with a multistage pore structure is finally formed; when the obtained hierarchical pore material is used as a catalyst for preparing carbon monoxide by electrochemical reduction of carbon dioxide, the transportation of materials in pore channels and the exposure of active sites can be improved, so that the reaction kinetics in the carbon dioxide conversion process can be improved, and the Faraday efficiency and the current distribution density of the carbon monoxide are improved.
Drawings
FIG. 1 is a STEM chart of a hierarchical pore material obtained in example 1;
FIG. 2 is an SEM image of a hierarchical pore material obtained in example 1;
FIG. 3 is a schematic diagram of the synthetic route of example 1;
FIG. 4 is a graph showing the Faraday efficiency of carbon monoxide in the preparation of carbon monoxide by catalytic reduction of carbon dioxide using the hierarchical pore material obtained in example 1 as a catalyst;
FIG. 5 is a graph showing the current density distribution when carbon dioxide is reduced to carbon monoxide using the hierarchical pore material obtained in example 1 as a catalyst.
Detailed Description
The invention provides a preparation method of a hierarchical pore material, which comprises the following steps:
mixing a template agent, a surface modifier and a polar solvent to obtain a matrix material;
growing metal organic compounds on the surface of the matrix material in situ to obtain a precursor material;
sequentially roasting and acid leaching the precursor material to obtain the hierarchical pore material;
the template agent has a loose porous structure;
the template agent comprises one or more of metal oxide, metal salt and silicon oxide.
In the present invention, all the preparation materials are commercially available products well known to those skilled in the art unless specified otherwise.
The invention mixes the template agent, the surface modifier and the polar solvent to obtain the matrix material.
In the present invention, the templating agent has a porous structure. In the present invention, the template agent includes one or more of a metal oxide, a metal salt, and an oxide of silicon. In the present invention, the metal oxide preferably includes magnesium oxide and/or zinc oxide. In the present invention, the metal salt preferably includes basic magnesium carbonate. In the present invention, the oxide of silicon preferably includes silicon dioxide. When the template is two or more of the above-mentioned choices, the proportion of the specific substance is not particularly limited, and the specific substance may be mixed in any proportion.
In the present invention, the surface modifier preferably includes one or more of polyvinylpyrrolidone, dodecyltrimethylammonium bromide, dicetyltrimethylammonium bromide, and sodium dodecyl sulfonate; when the surface modifier is two or more of the above-mentioned choices, the proportion of the specific substances is not particularly limited, and the specific substances may be mixed in any proportion.
In the present invention, the polar solvent preferably includes one or more of methanol, ethanol, dimethyl sulfoxide, N-dimethylformamide and water; when the polar solvent is two or more of the above-mentioned choices, the proportion of the specific substance is not particularly limited, and the specific substance may be mixed in any proportion.
In the invention, the mass ratio of the surface modifier to the template agent is preferably 1: 10-10: 1, further preferably 1:9 to 9:1, more preferably 1: 8-8: 1.
in the invention, the dosage ratio of the template agent to the polar solvent is preferably 0.5-50 mg:1mL, more preferably 5 to 45mg:1mL, more preferably 10 to 40mg:1mL.
In the present invention, the mixing is preferably performed under room temperature conditions. In the present invention, the mixing preferably includes sequentially performing ultrasonic and stirring. In the present invention, the power of the ultrasound is preferably 200 to 3000W, more preferably 500 to 2500W, and still more preferably 1000 to 2000W; the time is preferably 30 minutes. In the present invention, the rotation speed of the stirring is preferably 100 to 10000rpm, more preferably 500 to 9000rpm, still more preferably 1000 to 8000rpm; the time is preferably 6 hours. After the mixing is completed, the present invention also preferably includes centrifuging the resulting mixture. The process of separation and centrifugation is not particularly limited in the present invention, and may be carried out by a process known to those skilled in the art.
After the matrix material is obtained, the metal organic compound grows in situ on the surface of the matrix material to obtain the precursor material.
In the present invention, the metal organic compound preferably has a porous structure.
In the present invention, the metal organic compound preferably includes a zeolite imidazole framework or a metal organic complex.
In the present invention, when the metal organic compound is a zeolite imidazole framework, the in-situ growth preferably includes the steps of: mixing the matrix material, the first soluble metal salt, the second soluble metal salt, the 2-methylimidazole and the polar solvent, and carrying out a meridian reaction to obtain a precursor material.
In the present invention, the first soluble metal salt is preferably a soluble zinc salt; the soluble zinc salt preferably comprises one or more of zinc nitrate, zinc chloride, zinc sulfate, zinc acetonate and zinc acetate; when the soluble zinc salt is two or more of the above-mentioned choices, the ratio of the specific substances is not particularly limited, and the soluble zinc salt may be mixed in any ratio. In a specific embodiment of the invention, the zinc nitrate is preferably added in the form of zinc nitrate hexahydrate.
In the present invention, the second soluble metal salt preferably includes one or more of a soluble nickel salt, a soluble iron salt, a soluble cobalt salt, a soluble copper salt, a soluble manganese salt, a soluble ruthenium salt, and a soluble silver salt; when the second soluble metal salt is two or more of the above-mentioned choices, the proportion of the specific substance is not particularly limited, and the second soluble metal salt may be mixed in any proportion.
In the present invention, the soluble nickel salt preferably includes one or more of nickel nitrate, nickel citrate, nickel acetate, nickel sulfate and nickel chloride; when the soluble nickel salt is two or more of the above-mentioned choices, the ratio of the specific substances is not particularly limited, and the soluble nickel salt may be mixed in any ratio. In a specific embodiment of the invention, the nickel nitrate is preferably added in the form of nickel nitrate hexahydrate.
In the present invention, the soluble iron salt preferably includes one or more of ferric nitrate, ferric ammonium citrate, ferric acetate, ferric acetylacetonate, ferric sulfate, ferrocene, ferric chloride, ferrous acetate, ferrous nitrate, ferrous sulfate, ferrous lactate, ferrous chloride and ferrous citrate; when the soluble iron salt is two or more of the above-mentioned choices, the ratio of the specific substances is not particularly limited, and the soluble iron salt may be mixed in any ratio. In a specific embodiment of the invention, the ferric nitrate is preferably added as ferric nitrate nonahydrate.
In the present invention, the soluble cobalt salt preferably includes one or more of cobalt nitrate, cobalt citrate, cobalt acetate, cobalt sulfate and cobalt chloride; when the soluble cobalt salt is two or more of the above specific choices, the ratio of the specific substances is not particularly limited in the present invention, and the soluble cobalt salt may be mixed in any ratio. In a specific embodiment of the invention, the cobalt nitrate is preferably added in the form of cobalt nitrate hexahydrate.
In the present invention, the soluble copper salt preferably includes one or more of copper nitrate, copper acetate, copper sulfate, copper chloride, copper acetate, copper nitrate, copper sulfate and copper chloride; when the soluble copper salt is two or more of the above specific choices, the ratio of the specific substances is not particularly limited in the present invention, and the soluble copper salt may be mixed in any ratio. In the present invention, the copper nitrate is preferably added as copper nitrate hexahydrate.
In the present invention, the soluble manganese salt preferably includes one or more of manganese nitrate, manganese citrate, manganese acetate, manganese sulfate and manganese chloride; when the soluble manganese salt is two or more of the above specific choices, the ratio of the specific substances is not particularly limited in the present invention, and the soluble manganese salt may be mixed in any ratio. In the present invention, the manganese nitrate is preferably added in the form of manganese nitrate hexahydrate.
In the present invention, the soluble ruthenium salt preferably includes one or more of ruthenium chloride, ruthenium acetate and ruthenium dicyclopentadiene; when the soluble ruthenium salt is two or more of the above specific choices, the ratio of the specific substances is not particularly limited in the present invention, and the soluble ruthenium salt may be mixed in any ratio. In the present invention, the soluble silver salt preferably includes silver nitrate.
In the present invention, the polar solvent preferably includes one or more of methanol, ethanol, dimethyl sulfoxide, N-dimethylformamide and water; when the polar solvent is two or more of the above specific choices, the proportion of the specific substances is not particularly limited, and the polar solvent may be mixed in any proportion.
In the present invention, the mass ratio of the second soluble metal salt to the first soluble metal salt is preferably 1: 20-20: 1, further preferably 1: 17-17: 1, more preferably 1: 15-15: 1. in the present invention, the ratio of the first soluble metal salt to the polar solvent is preferably 0.5 to 50mg:1mL, more preferably 5 to 45mg:1mL, more preferably 10 to 40mg:1mL.
The mixing process is not particularly limited, and may be performed by a process well known to those skilled in the art.
In a specific embodiment of the present invention, the mixing process preferably includes: first mixing a matrix material and a first polar solvent to obtain a first mixed solution; second mixing the first soluble metal salt, the second soluble metal salt and the second polar solvent to obtain a second mixed solution; thirdly mixing the 2-methylimidazole with a third polar solvent to obtain a third mixed solution; and dripping the second mixed solution and the third mixed solution into the first mixed solution.
In the present invention, the types of the first polar solvent, the second polar solvent and the third polar solvent are the same as those defined above, and will not be described here again.
In the present invention, the total volume of the first polar solvent, the second polar solvent and the third polar solvent is the same as the volume of the polar solvent defined in the above technical scheme.
In the present invention, the ratio of the base material to the first polar solvent is preferably 0.5 to 100mg:1mL, more preferably 20 to 80mg:1mL. In the present invention, the ratio of the first soluble metal salt to the second polar solvent is preferably 0.5 to 100mg:1mL, more preferably 20 to 50mg:1mL. In the present invention, the dosage ratio of the 2-methylimidazole and the third polar solvent is preferably 0.5 to 100mg:1mL, more preferably 20 to 50mg:1mL.
The process of the first, second and third mixing is not particularly limited, and may be performed by a process well known to those skilled in the art.
In the present invention, the dropping speed of the second mixed solution and the third mixed solution is independently preferably 2 to 10mL/min, more preferably 5mL/min.
In the present invention, the temperature of the complexation reaction is preferably 20 to 200 ℃, more preferably 40 to 180 ℃, still more preferably 60 to 160 ℃; the time is preferably 6 to 48 hours, more preferably 10 to 40 hours, and still more preferably 15 to 35 hours. In the present invention, the complexing reaction is preferably carried out under stirring; the rotation speed of the stirring is preferably 100 to 10000rpm, more preferably 300 to 9000rpm, and still more preferably 800 to 8000rpm. In the present invention, the complexing reaction is preferably carried out under reflux conditions.
After the completion of the complexation reaction, the present invention also preferably includes subjecting the obtained product to centrifugal separation, drying and grinding. The process of centrifugal separation and grinding is not particularly limited, and may be performed by a process well known to those skilled in the art. In the present invention, the temperature of the drying is preferably 70 ℃; the time is preferably 12 hours. In the present invention, the drying is preferably performed in a vacuum oven.
In the present invention, when the metal organic compound is a metal organic complex, the in-situ growth preferably includes the steps of:
mixing a matrix material, soluble metal salt, an organic ligand and a polar solvent, and carrying out a meridian combination reaction to obtain the precursor material.
In the present invention, the soluble metal salt preferably includes one or more of a soluble nickel salt, a soluble iron salt, a soluble cobalt salt, a soluble copper salt, a soluble manganese salt, a soluble ruthenium salt, and a soluble silver salt.
In the present invention, the soluble nickel salt preferably includes one or more of nickel nitrate, nickel citrate, nickel acetate, nickel sulfate and nickel chloride; when the soluble nickel salt is two or more of the above-mentioned choices, the ratio of the specific substances is not particularly limited, and the soluble nickel salt may be mixed in any ratio. In a specific embodiment of the invention, the nickel nitrate is preferably added in the form of nickel nitrate hexahydrate.
In the present invention, the soluble iron salt preferably includes one or more of ferric nitrate, ferric ammonium citrate, ferric acetate, ferric acetylacetonate, ferric sulfate, ferrocene, ferric chloride, ferrous acetate, ferrous nitrate, ferrous sulfate, ferrous lactate, ferrous chloride and ferrous citrate; when the soluble iron salt is two or more of the above-mentioned choices, the ratio of the specific substances is not particularly limited, and the soluble iron salt may be mixed in any ratio. In a specific embodiment of the invention, the ferric nitrate is preferably added as ferric nitrate nonahydrate.
In the present invention, the soluble cobalt salt preferably includes one or more of cobalt nitrate, cobalt citrate, cobalt acetate, cobalt sulfate and cobalt chloride; when the soluble cobalt salt is two or more of the above specific choices, the ratio of the specific substances is not particularly limited in the present invention, and the soluble cobalt salt may be mixed in any ratio. In a specific embodiment of the invention, the cobalt nitrate is preferably added in the form of cobalt nitrate hexahydrate.
In the present invention, the soluble copper salt preferably includes one or more of copper nitrate, copper acetate, copper sulfate, copper chloride, copper acetate, copper nitrate, copper sulfate and copper chloride; when the soluble copper salt is two or more of the above specific choices, the ratio of the specific substances is not particularly limited in the present invention, and the soluble copper salt may be mixed in any ratio. In the present invention, the copper nitrate is preferably added as copper nitrate hexahydrate.
In the present invention, the soluble manganese salt preferably includes one or more of manganese nitrate, manganese citrate, manganese acetate, manganese sulfate and manganese chloride; when the soluble manganese salt is two or more of the above specific choices, the ratio of the specific substances is not particularly limited in the present invention, and the soluble manganese salt may be mixed in any ratio. In the present invention, the manganese nitrate is preferably added in the form of manganese nitrate hexahydrate.
In the present invention, the soluble ruthenium salt preferably includes one or more of ruthenium chloride, ruthenium acetate and ruthenium dicyclopentadiene; when the soluble ruthenium salt is two or more of the above specific choices, the ratio of the specific substances is not particularly limited in the present invention, and the soluble ruthenium salt may be mixed in any ratio. In the present invention, the soluble silver salt preferably includes silver nitrate.
In the invention, the organic ligand preferably comprises one or more of phenanthroline, formamide, melamine and polyaniline; when the organic ligand is two or more of the above-mentioned choices, the ratio of the specific substances is not particularly limited, and the organic ligand may be mixed in any ratio.
In the present invention, the polar solvent preferably includes one or more of methanol, ethanol, dimethyl sulfoxide, N-dimethylformamide and water; when the polar solvent is two or more of the above specific choices, the proportion of the specific substances is not particularly limited, and the polar solvent may be mixed in any proportion.
In the present invention, the mass ratio of the soluble metal salt to the organic ligand is preferably 1: 50-50: 1, further preferably 1: 30-30: 1, more preferably 1: 20-20: 1. in the present invention, the ratio of the soluble metal salt to the polar solvent is preferably 0.5 to 500mg:1mL, more preferably 10 to 450mg:1mL, more preferably 50 to 400mg:1mL.
The mixing process is not particularly limited, and may be performed by a process well known to those skilled in the art.
In a specific embodiment of the present invention, the mixing process preferably includes: fourth mixing the matrix material and the fourth polar solvent to obtain a fourth mixed solution; fifth mixing the soluble metal salt and a fifth polar solvent to obtain a fifth mixed solution; sixth mixing the organic ligand and a sixth polar solvent to obtain a sixth mixed solution; and dripping the fifth mixed solution and the sixth mixed solution into the fourth mixed solution.
In the present invention, the fourth polar solvent, the fifth polar solvent and the sixth polar solvent are the same as the above-defined polar solvents, and will not be described herein.
In the present invention, the total volume of the fourth polar solvent, the fifth polar solvent and the sixth polar solvent is the same as the volume of the polar solvent defined in the above-mentioned technical scheme.
In the present invention, the ratio of the base material to the fourth polar solvent is preferably 0.5 to 100mg:1mL, more preferably 10 to 80mg:1mL. In the present invention, the ratio of the soluble metal salt to the fifth polar solvent is preferably 0.5 to 100mg:1mL, more preferably 10 to 80mg:1mL. In the present invention, the ratio of the organic ligand to the sixth polar solvent is preferably 0.5 to 100mg:1mL, more preferably 10 to 80mg:1mL.
The fourth mixing, fifth mixing and sixth mixing processes are not particularly limited, and may be performed by processes well known to those skilled in the art.
In the present invention, the dropping speed of the fifth mixed solution and the sixth mixed solution is independently preferably 2 to 10mL/min, more preferably 5mL/min.
In the present invention, the temperature of the complexation reaction is preferably 20 to 200 ℃, more preferably 40 to 180 ℃, still more preferably 60 to 160 ℃; the time is preferably 6 to 48 hours, more preferably 10 to 40 hours, and still more preferably 15 to 35 hours. In the present invention, the complexing reaction is preferably carried out under stirring; the rotation speed of the stirring is preferably 100 to 10000rpm, more preferably 300 to 9000rpm, and still more preferably 800 to 8000rpm. In the present invention, the complexing reaction is preferably carried out under reflux conditions.
After the completion of the complexation reaction, the present invention also preferably includes subjecting the obtained product to centrifugal separation, drying and grinding. The process of centrifugal separation and grinding is not particularly limited, and may be performed by a process well known to those skilled in the art. In the present invention, the temperature of the drying is preferably 70 ℃; the time is preferably 12 hours. In the present invention, the drying is preferably performed in a vacuum oven.
After the precursor material is obtained, the precursor material is subjected to roasting and acid leaching treatment to obtain the hierarchical pore material.
In the present invention, the temperature of the calcination is preferably 600 to 1200 ℃, more preferably 700 to 1100 ℃, still more preferably 800 to 1000 ℃; the heating rate for heating to the roasting temperature is preferably 10 ℃/min; the holding time is preferably 0.5 to 10 hours, more preferably 1 to 9 hours, and still more preferably 2 to 8 hours. In the present invention, the firing is preferably performed under a protective atmosphere; the protective atmosphere preferably comprises one or more of nitrogen, argon, helium and neon; when the protective atmosphere is two or more of the above choices, the ratio of the specific substances is not particularly limited, and the specific substances may be mixed in any ratio. In the invention, the introducing rate of the protective atmosphere is preferably 80mL/min. In the present invention, the firing is preferably performed in a tube furnace.
After the calcination is completed, the present invention also preferably includes cooling the resulting product to room temperature. The process of cooling to room temperature is not particularly limited in the present invention, and may be employed as is well known to those skilled in the art.
In the invention, the acidic reagent used in the acid leaching treatment preferably comprises one or more of sulfuric acid, hydrochloric acid and hydrofluoric acid; when the acidic reagent is two or more of the above-mentioned choices, the ratio of the specific substances is not particularly limited, and the specific substances may be mixed in any ratio.
In the present invention, when the template is an oxide of silicon, the acidic reagent is preferably hydrofluoric acid.
In the present invention, the concentration of the acidic reagent is preferably 0.5 to 5mol/L, more preferably 2mol/L. The amount of the acidic reagent used in the present invention is not particularly limited, and the template agent may be removed.
In the present invention, the acid leaching treatment is preferably performed under stirring; the rotation speed of the stirring is preferably 100 to 10000rpm, more preferably 300 to 9000rpm, and still more preferably 800 to 8000rpm; the time is preferably 24 hours. In the present invention, the template agent can be removed by acid leaching treatment.
After the acid leaching treatment is completed, the present invention also preferably includes filtering and drying the obtained product.
The filtering process is not particularly limited, and may be performed by a process well known to those skilled in the art. In the present invention, the temperature of the drying is preferably 70℃and the time is preferably 10 hours.
As another embodiment of the present invention, the templating agent is replaced with polystyrene. In the present invention, when the template is polystyrene, the preparation method of the hierarchical pore material does not include acid leaching treatment. In the present invention, when the template is polystyrene, the template is preferably removed during firing.
The invention also provides the hierarchical pore material prepared by the preparation method of the technical scheme, and the hierarchical pore material is a metal doped hierarchical pore carbon material.
In the present invention, the metal preferably includes one or more of nickel, iron, cobalt, copper, manganese, ruthenium and silver. In the present invention, the metal content is preferably 0.5 to 15.0% by mass, more preferably 1.0 to 14.0% by mass, and still more preferably 2.0 to 13.0% by mass.
In the present invention, the doping element of the hierarchical pore carbon material further preferably includes nitrogen. In the present invention, the nitrogen content is preferably 5.0 to 15.0% by mass, more preferably 6.0 to 14.0% by mass, and still more preferably 7.0 to 13.0% by mass.
In the present invention, the metal (M) on the hierarchical pore carbon material is preferably in the form of M-N 4 Unit (B)The form of dots exists.
According to the invention, the electronic structure of the hierarchical pore material can be regulated by doping metal and nitrogen elements in the hierarchical pore material, so that the catalytic activity of the hierarchical pore material is improved from a thermodynamic level; by combining the arrangement of the multistage pore structure, the reaction kinetics in the carbon dioxide conversion process can be further improved, and the Faraday efficiency and the current-dividing density of the carbon monoxide are improved.
In the present invention, the specific surface area of the hierarchical pore material is preferably 500 to 2000m 2 Preferably 600 to 1900m 2 Preferably 700 to 1800m 2 /g; the pore volume is preferably 0.2 to 2cm 3 Preferably 0.5 to 1.5 cm/g 3 Preferably 0.8 to 1.2cm per gram 3 And/g. In the present invention, the multistage pore preferably includes a microporous structure, a mesoporous structure, and a macroporous structure. In the present invention, the pore volume ratio of the microporous structure, the mesoporous structure and the macroporous structure is preferably 1: (0.5-5): (0.5 to 5), more preferably 1: (2-3): (2-3).
The invention also provides application of the hierarchical porous material in catalyzing carbon dioxide reduction reaction.
In the present invention, the application preferably includes the steps of:
mixing the hierarchical pore material, ethanol and perfluorinated sulfonic acid type polymer solution to obtain slurry; the mass concentration of the perfluorinated sulfonic acid type polymer solution is preferably 5%; the dosage ratio of the hierarchical pore material, ethanol and perfluorosulfonic acid type polymer solution is preferably 1.2mg:564 μl: 36. Mu.L;
coating the slurry on a surface of 1X 3cm 2 On carbon paper (load of 0.4 mg/cm) 2 ) Obtaining a catalyst electrode (i.e. a working electrode);
The catalyst electrode is used as a cathode, a KOH solution with the concentration of 1mol/L is used as an electrolyte, an Ag/AgCl electrode (a KCl solution with the concentration of 3mol/L solvent) is used as a reference electrode, foam nickel is used as a counter electrode, and an anion exchange membrane is used as a diaphragm, so that the gas diffusion electrode is assembled. Setting the water circulation rotating speed to be 30mL/min under the conditions of normal temperature and normal pressure; at 20Rate of mL/min CO 2 Air flow for 20min to make CO 2 The gas is saturated, cyclic voltammetry scanning is carried out for 30 circles, and the catalyst is activated and the absorbed gas is discharged; after 12min of power on stabilization, 1mL of gas is extracted for gas chromatography detection, H 2 The CO was detected by a Thermal Conductivity Detector (TCD) in the chromatograph, a hydrogen Flame Ionization Detector (FID) equipped with a nickel reformer, and the faraday efficiency and split current density of the product were calculated from the measured product gas content.
For further explanation of the present invention, a hierarchical pore material, a method for preparing the same and applications thereof, provided by the present invention, are described in detail below with reference to the accompanying drawings and examples, which should not be construed as limiting the scope of the present invention.
Example 1
Mixing 500mg of basic magnesium carbonate with a loose porous structure, 500mg of polyvinylpyrrolidone and 100mL of methanol, sequentially carrying out ultrasonic treatment at 500W for 30min at normal temperature and stirring at a stirring speed of 300rpm for 6h, centrifuging by a centrifuge, and taking out a lower precipitate to obtain 621mg of matrix material;
Uniformly stirring and dispersing the obtained matrix material and 250mL of methanol to obtain a first mixed solution; mixing 850mg of zinc nitrate hexahydrate, 50mg of nickel nitrate hexahydrate and 25mL of methanol for dissolution to obtain a second mixed solution; 1g of 2-methylimidazole and 25mL of methanol are mixed and dissolved to obtain a third mixed solution; dripping the second mixed solution and the third mixed solution into the first mixed solution at a dripping speed of 5mL/min, putting the obtained mixed solution into an oil bath kettle, heating and refluxing, and carrying out complexation reaction for 12h at 60 ℃; centrifuging the mixture by using a centrifuge after the reaction is finished, taking out a lower precipitate, putting the lower precipitate into a vacuum oven at 70 ℃ for drying for 12 hours, taking out the lower precipitate, and grinding the lower precipitate into powder to obtain a precursor material;
placing the obtained precursor material into a tube furnace, heating to 900 ℃ at a heating rate of 10 ℃/min under the protection of 80mL/min nitrogen gas flow, and roasting for 2h; cooling to room temperature after roasting; mixing the cooled product with 100mL of sulfuric acid solution with the concentration of 2mol/L, stirring at the stirring speed of 300rpm for 24 hours at room temperature, carrying out acid leaching treatment, and dissolving out a template agent; then filtering and drying for 10 hours at 70 ℃ to obtain the nickel-nitrogen doped hierarchical pore carbon material;
The synthetic route diagram of this embodiment is shown in FIG. 3;
the nickel-nitrogen doped hierarchical pore carbon material obtained in this example had a nickel loading of 1.8wt.%, a nitrogen content of 7.8wt.%, and a specific surface area of 672m 2 Per gram, pore volume of 1.49cm 3 /g (wherein the pore volume ratio of microporous, mesoporous and macroporous structures is 1:2:3).
Example 2
Mixing 500mg of basic magnesium carbonate with a loose porous structure, 500mg of sodium dodecyl sulfate and 100mL of methanol, sequentially carrying out ultrasonic treatment at 500W for 30min at normal temperature and stirring at a stirring speed of 300rpm for 6h, centrifuging by a centrifuge, and taking out a lower precipitate to obtain 634mg of matrix material;
uniformly stirring and dispersing the obtained matrix material and 250mL of methanol to obtain a first mixed solution; mixing 850mg of zinc nitrate hexahydrate, 50mg of nickel nitrate hexahydrate and 25mL of methanol for dissolution to obtain a second mixed solution; 1g of 2-methylimidazole and 25mL of methanol are mixed and dissolved to obtain a third mixed solution; dripping the second mixed solution and the third mixed solution into the first mixed solution at a dripping speed of 5mL/min, putting the obtained mixed solution into an oil bath kettle, heating and refluxing, and carrying out complexation reaction for 12h at 60 ℃; centrifuging the mixture by using a centrifuge after the reaction is finished, taking out a lower precipitate, putting the lower precipitate into a vacuum oven at 70 ℃ for drying for 12 hours, taking out the lower precipitate, and grinding the lower precipitate into powder to obtain a precursor material;
Placing the obtained precursor material into a tube furnace, heating to 900 ℃ at a heating rate of 10 ℃/min under the protection of 80mL/min nitrogen gas flow, and roasting for 2h; cooling to room temperature after roasting; mixing the cooled product with 100mL of sulfuric acid solution with the concentration of 2mol/L, stirring at the stirring speed of 300rpm for 24 hours at room temperature, carrying out acid leaching treatment, and dissolving out a template agent; then filtering and drying for 10 hours at 70 ℃ to obtain the nickel-nitrogen doped hierarchical pore carbon material;
the nickel-nitrogen doped hierarchical pore carbon material obtained in this example had a nickel loading of 1.7wt.%, and a nitrogen content of 1.7wt.%7.5wt.% with a specific surface area of 654m 2 Per gram, pore volume of 1.46cm 3 /g (wherein the pore volume ratio of microporous, mesoporous and macroporous structures is 1:2:2).
Example 3
Mixing 500mg of zinc oxide with a loose porous structure, 500mg of polyvinylpyrrolidone and 100mL of methanol, sequentially carrying out ultrasonic treatment at 500W for 30min at normal temperature and stirring at a stirring speed of 300rpm for 6h, centrifuging by a centrifuge, and taking out a lower precipitate to obtain 586mg of matrix material;
uniformly stirring and dispersing the obtained matrix material and 250mL of methanol to obtain a first mixed solution; mixing 850mg of zinc nitrate hexahydrate, 50mg of nickel nitrate hexahydrate and 25mL of methanol for dissolution to obtain a second mixed solution; 1g of 2-methylimidazole and 25mL of methanol are mixed and dissolved to obtain a third mixed solution; dripping the second mixed solution and the third mixed solution into the first mixed solution at a dripping speed of 5mL/min, putting the obtained mixed solution into an oil bath kettle, heating and refluxing, and carrying out complexation reaction for 12h at 60 ℃; centrifuging the mixture by using a centrifuge after the reaction is finished, taking out a lower precipitate, putting the lower precipitate into a vacuum oven at 70 ℃ for drying for 12 hours, taking out the lower precipitate, and grinding the lower precipitate into powder to obtain a precursor material;
Placing the obtained precursor material into a tube furnace, heating to 900 ℃ at a heating rate of 10 ℃/min under the protection of 80mL/min nitrogen gas flow, and roasting for 2h; cooling to room temperature after roasting; mixing the cooled product with 100mL of sulfuric acid solution with the concentration of 2mol/L, stirring at the stirring speed of 300rpm for 24 hours at room temperature, carrying out acid leaching treatment, and dissolving out a template agent; then filtering and drying for 10 hours at 70 ℃ to obtain the nickel-nitrogen doped hierarchical pore carbon material;
the nickel-nitrogen doped hierarchical pore carbon material obtained in this example had a nickel loading of 1.7wt.%, a nitrogen content of 7.2wt.%, and a specific surface area of 658m 2 Per gram, pore volume of 1.37cm 3 /g (wherein the pore volume ratio of microporous, mesoporous and macroporous structures is 1:1:2).
Example 4
Mixing 500mg of basic magnesium carbonate with a loose porous structure, 500mg of polyvinylpyrrolidone and 100mL of methanol, sequentially carrying out ultrasonic treatment at 500W for 30min at normal temperature and stirring at a stirring speed of 300rpm for 6h, centrifuging by a centrifuge, and taking out a lower precipitate to obtain 623mg of matrix material;
uniformly stirring and dispersing the obtained matrix material and 250mLN, N-dimethylformamide to obtain a first mixed solution; mixing and dissolving 850mg of zinc nitrate hexahydrate, 50mg of nickel nitrate hexahydrate and 25mLN, N-dimethylformamide to obtain a second mixed solution; 1g of 2-methylimidazole and 25mLN, N-dimethylformamide are mixed and dissolved to obtain a third mixed solution; dripping the second mixed solution and the third mixed solution into the first mixed solution at a dripping speed of 5mL/min, putting the obtained mixed solution into an oil bath kettle, heating and refluxing, and carrying out complexation reaction for 12h at 120 ℃; centrifuging the mixture by using a centrifuge after the reaction is finished, taking out a lower precipitate, putting the lower precipitate into a vacuum oven at 70 ℃ for drying for 12 hours, taking out the lower precipitate, and grinding the lower precipitate into powder to obtain a precursor material;
Placing the obtained precursor material into a tube furnace, heating to 900 ℃ at a heating rate of 10 ℃/min under the protection of 80mL/min nitrogen gas flow, and roasting for 2h; cooling to room temperature after roasting; mixing the cooled product with 100mL of sulfuric acid solution with the concentration of 2mol/L, stirring at the stirring speed of 300rpm for 24 hours at room temperature, carrying out acid leaching treatment, and dissolving out a template agent; then filtering and drying for 10 hours at 70 ℃ to obtain the nickel-nitrogen doped hierarchical pore carbon material;
the nickel-nitrogen doped hierarchical pore carbon material obtained in this example had a nickel loading of 1.2wt.%, a nitrogen content of 6.9wt.%, and a specific surface area of 608m 2 Per gram, pore volume of 1.35cm 3 /g (wherein the pore volume ratio of microporous, mesoporous and macroporous structures is 1:1:3).
Example 5
Mixing 500mg of basic magnesium carbonate with a loose porous structure, 500mg of polyvinylpyrrolidone and 100mL of methanol, sequentially carrying out ultrasonic treatment at 500W for 30min at normal temperature and stirring at a stirring speed of 300rpm for 6h, centrifuging by a centrifuge, and taking out a lower precipitate to obtain 618mg of matrix material;
uniformly stirring and dispersing the obtained precursor material and 250mL of methanol to obtain a fourth mixed solution; mixing 50mg of nickel nitrate hexahydrate and 25mL of methanol for dissolution to obtain a fifth mixed solution; mixing and dissolving 1g of phenanthroline and 25mL of methanol to obtain a sixth mixed solution; dripping the fifth mixed solution and the sixth mixed solution into the fourth mixed solution at a dripping speed of 5mL/min, putting the obtained mixed solution into an oil bath kettle, heating and refluxing, and carrying out complexation reaction for 12h at 60 ℃; centrifuging the mixture by using a centrifuge after the reaction is finished, taking out a lower precipitate, putting the lower precipitate into a vacuum oven at 70 ℃ for drying for 12 hours, taking out the lower precipitate, and grinding the lower precipitate into powder to obtain a precursor material;
Placing the obtained precursor material into a tube furnace, heating to 900 ℃ at a heating rate of 10 ℃/min under the protection of 80mL/min nitrogen gas flow, and roasting for 2h; cooling to room temperature after roasting; mixing the cooled product with 100mL of sulfuric acid solution with the concentration of 2mol/L, stirring at the stirring speed of 300rpm for 24 hours at room temperature, carrying out acid leaching treatment, and dissolving out a template agent; then filtering and drying for 10 hours at 70 ℃ to obtain the nickel-nitrogen doped hierarchical pore carbon material;
the nickel-nitrogen doped hierarchical pore carbon material obtained in this example had a nickel loading of 1.2wt.%, a nitrogen content of 7.1wt.%, and a specific surface area of 629m 2 Per gram, pore volume of 1.68cm 3 /g (wherein the pore volume ratio of microporous, mesoporous and macroporous structures is 1:0.5:2).
Example 6
Mixing 500mg of basic magnesium carbonate with a loose porous structure, 500mg of polyvinylpyrrolidone and 100mL of methanol, sequentially carrying out ultrasonic treatment at 500W for 30min at normal temperature and stirring at a stirring speed of 300rpm for 6h, centrifuging by a centrifuge, and taking out a lower precipitate to obtain 615mg of matrix material;
uniformly stirring and dispersing the obtained matrix material and 250mL of methanol to obtain a first mixed solution; mixing 850mg of zinc nitrate hexahydrate, 50mg of ferric nitrate nonahydrate and 25mL of methanol for dissolution to obtain a second mixed solution; 1g of 2-methylimidazole and 25mL of methanol are mixed and dissolved to obtain a third mixed solution; dripping the second mixed solution and the third mixed solution into the first mixed solution at a dripping speed of 5mL/min, putting the obtained mixed solution into an oil bath kettle, heating and refluxing, and carrying out complexation reaction for 12h at 60 ℃; centrifuging the mixture by using a centrifuge after the reaction is finished, taking out a lower precipitate, putting the lower precipitate into a vacuum oven at 70 ℃ for drying for 12 hours, taking out the lower precipitate, and grinding the lower precipitate into powder to obtain a precursor material;
Placing the obtained precursor material into a tube furnace, heating to 900 ℃ at a heating rate of 10 ℃/min under the protection of 80mL/min nitrogen gas flow, and roasting for 2h; cooling to room temperature after roasting; mixing the cooled product with 100mL of sulfuric acid solution with the concentration of 2mol/L, stirring at the stirring speed of 300rpm for 24 hours at room temperature, carrying out acid leaching treatment, and dissolving out a template agent; then filtering and drying for 10 hours at 70 ℃ to obtain the Fe-N doped hierarchical pore carbon material;
the iron-nitrogen doped hierarchical pore carbon material obtained in this example had an iron loading of 1.82wt.%, a nitrogen content of 7.7wt.%, and a specific surface area of 696m 2 Per gram, pore volume of 1.79cm 3 /g (wherein the pore volume ratio of microporous, mesoporous and macroporous structures is 1:3:2).
Example 7
Mixing 500mg of basic magnesium carbonate with a loose porous structure, 500mg of polyvinylpyrrolidone and 100mL of methanol, sequentially carrying out ultrasonic treatment at 500W for 30min at normal temperature and stirring at a stirring speed of 300rpm for 6h, centrifuging by a centrifuge, and taking out a lower precipitate to obtain 609mg of matrix material;
uniformly stirring and dispersing the obtained matrix material and 250mL of methanol to obtain a first mixed solution; mixing 850mg of zinc nitrate hexahydrate, 50mg of cobalt nitrate hexahydrate and 25mL of methanol for dissolution to obtain a second mixed solution; 1g of 2-methylimidazole and 25mL of methanol are mixed and dissolved to obtain a third mixed solution; dripping the second mixed solution and the third mixed solution into the first mixed solution at a dripping speed of 5mL/min, putting the obtained mixed solution into an oil bath kettle, heating and refluxing, and carrying out complexation reaction for 12h at 60 ℃; centrifuging the mixture by using a centrifuge after the reaction is finished, taking out a lower precipitate, putting the lower precipitate into a vacuum oven at 70 ℃ for drying for 12 hours, taking out the lower precipitate, and grinding the lower precipitate into powder to obtain a precursor material;
Placing the obtained precursor material into a tube furnace, heating to 900 ℃ at a heating rate of 10 ℃/min under the protection of 80mL/min nitrogen gas flow, and roasting for 2h; cooling to room temperature after roasting; mixing the cooled product with 100mL of sulfuric acid solution with the concentration of 2mol/L, stirring at the stirring speed of 300rpm for 24 hours at room temperature, carrying out acid leaching treatment, and dissolving out a template agent; then filtering and drying for 10 hours at 70 ℃ to obtain a cobalt-nitrogen doped hierarchical pore carbon material;
the cobalt-nitrogen doped hierarchical pore carbon material obtained in this example had a cobalt loading of 1.08wt.%, a nitrogen content of 8.6wt.%, and a specific surface area of 702m 2 Per gram, pore volume of 1.82cm 3 /g (wherein the pore volume ratio of microporous, mesoporous and macroporous structures is 1:0.5:3).
Example 8
Mixing 500mg of basic magnesium carbonate with a loose porous structure, 500mg of polyvinylpyrrolidone and 100mL of methanol, sequentially carrying out ultrasonic treatment at 500W for 30min at normal temperature and stirring at a stirring speed of 300rpm for 6h, centrifuging by a centrifuge, and taking out a lower precipitate to obtain 616mg of matrix material;
uniformly stirring and dispersing the obtained matrix material and 250mL of methanol to obtain a first mixed solution; mixing 850mg of zinc nitrate hexahydrate, 50mg of copper nitrate hexahydrate and 25mL of methanol for dissolution to obtain a second mixed solution; 1g of 2-methylimidazole and 25mL of methanol are mixed and dissolved to obtain a third mixed solution; dripping the second mixed solution and the third mixed solution into the first mixed solution at a dripping speed of 5mL/min, putting the obtained mixed solution into an oil bath kettle, heating and refluxing, and carrying out complexation reaction for 12h at 60 ℃; centrifuging the mixture by using a centrifuge after the reaction is finished, taking out a lower precipitate, putting the lower precipitate into a vacuum oven at 70 ℃ for drying for 12 hours, taking out the lower precipitate, and grinding the lower precipitate into powder to obtain a precursor material;
Placing the obtained precursor material into a tube furnace, heating to 900 ℃ at a heating rate of 10 ℃/min under the protection of 80mL/min nitrogen gas flow, and roasting for 2h; cooling to room temperature after roasting; mixing the cooled product with 100mL of sulfuric acid solution with the concentration of 2mol/L, stirring at the stirring speed of 300rpm for 24 hours at room temperature, carrying out acid leaching treatment, and dissolving out a template agent; then filtering and drying for 10 hours at 70 ℃ to obtain the copper-nitrogen doped hierarchical pore carbon material;
the copper-nitrogen doped hierarchical pore carbon material obtained in this example had a copper loading of 2.46wt.%, a nitrogen content of 5.1wt.%, and a specific surface area of 596m 2 Per gram, pore volume of 1.15cm 3 /g (wherein the pore volume ratio of microporous, mesoporous and macroporous structures is 1:2:1).
Example 9
Mixing 500mg of basic magnesium carbonate with a loose porous structure, 500mg of polyvinylpyrrolidone and 100mL of methanol, sequentially carrying out ultrasonic treatment at 500W for 30min at normal temperature and stirring at a stirring speed of 300rpm for 6h, centrifuging by a centrifuge, and taking out a lower precipitate to obtain 629mg of matrix material;
uniformly stirring and dispersing the obtained matrix material and 250mL of methanol to obtain a first mixed solution; mixing 850mg of zinc nitrate hexahydrate, 50mg of manganese nitrate hexahydrate and 25mL of methanol for dissolution to obtain a second mixed solution; 1g of 2-methylimidazole and 25mL of methanol are mixed and dissolved to obtain a third mixed solution; dripping the second mixed solution and the third mixed solution into the first mixed solution at a dripping speed of 5mL/min, putting the obtained mixed solution into an oil bath kettle, heating and refluxing, and carrying out complexation reaction for 12h at 60 ℃; centrifuging the mixture by using a centrifuge after the reaction is finished, taking out a lower precipitate, putting the lower precipitate into a vacuum oven at 70 ℃ for drying for 12 hours, taking out the lower precipitate, and grinding the lower precipitate into powder to obtain a precursor material;
Placing the obtained precursor material into a tube furnace, heating to 900 ℃ at a heating rate of 10 ℃/min under the protection of 80mL/min nitrogen gas flow, and roasting for 2h; cooling to room temperature after roasting; mixing the cooled product with 100mL of sulfuric acid solution with the concentration of 2mol/L, stirring at the stirring speed of 300rpm for 24 hours at room temperature, carrying out acid leaching treatment, and dissolving out a template agent; then filtering and drying for 10 hours at 70 ℃ to obtain the manganese-nitrogen doped hierarchical pore carbon material;
the manganese-nitrogen doped hierarchical pore carbon material obtained in this example had a manganese loading of 0.78wt.%, a nitrogen content of 10.4wt.%, and a specific surface area of 711m 2 Per gram, pore volume of 1.79cm 3 /g (wherein microporous structure, mesoporous structure andthe pore volume ratio of the macroporous structure is 1:2:2).
Example 10
Mixing 500mg of basic magnesium carbonate with a loose porous structure, 500mg of polyvinylpyrrolidone and 100mL of methanol, sequentially carrying out ultrasonic treatment at 500W for 30min at normal temperature, stirring at a stirring speed of 300rpm for 6h, centrifuging by a centrifuge, and taking out a lower precipitate to obtain 622mg of matrix material;
uniformly stirring and dispersing the obtained matrix material and 250mL of methanol to obtain a first mixed solution; mixing 850mg of zinc nitrate hexahydrate, 50mg of ruthenium chloride and 25mL of methanol for dissolution to obtain a second mixed solution; 1g of 2-methylimidazole and 25mL of methanol are mixed and dissolved to obtain a third mixed solution; dripping the second mixed solution and the third mixed solution into the first mixed solution at a dripping speed of 5mL/min, putting the obtained mixed solution into an oil bath kettle, heating and refluxing, and carrying out complexation reaction for 12h at 60 ℃; centrifuging the mixture by using a centrifuge after the reaction is finished, taking out a lower precipitate, putting the lower precipitate into a vacuum oven at 70 ℃ for drying for 12 hours, taking out the lower precipitate, and grinding the lower precipitate into powder to obtain a precursor material;
Placing the obtained precursor material into a tube furnace, heating to 900 ℃ at a heating rate of 10 ℃/min under the protection of 80mL/min nitrogen gas flow, and roasting for 2h; cooling to room temperature after roasting; mixing the cooled product with 100mL of sulfuric acid solution with the concentration of 2mol/L, stirring at the stirring speed of 300rpm for 24 hours at room temperature, carrying out acid leaching treatment, and dissolving out a template agent; then filtering and drying for 10 hours at 70 ℃ to obtain the ruthenium-nitrogen doped hierarchical pore carbon material;
the ruthenium-nitrogen doped hierarchical pore carbon material obtained in this example had a ruthenium loading of 0.64wt.%, a nitrogen content of 6.4wt.%, and a specific surface area of 634m 2 Per gram, pore volume of 1.28cm 3 /g (wherein the pore volume ratio of microporous, mesoporous and macroporous structures is 1:2:3).
Example 11
Mixing 500mg of basic magnesium carbonate with a loose porous structure, 500mg of polyvinylpyrrolidone and 100mL of methanol, sequentially carrying out ultrasonic treatment at 500W for 30min at normal temperature and stirring at a stirring speed of 300rpm for 6h, centrifuging by a centrifuge, and taking out a lower precipitate to obtain 604mg of matrix material;
uniformly stirring and dispersing the obtained matrix material and 250mL of methanol to obtain a first mixed solution; mixing 850mg of zinc nitrate hexahydrate, 50mg of silver nitrate and 25mL of methanol for dissolution to obtain a second mixed solution; 1g of 2-methylimidazole and 25mL of methanol are mixed and dissolved to obtain a third mixed solution; dripping the second mixed solution and the third mixed solution into the first mixed solution at a dripping speed of 5mL/min, putting the obtained mixed solution into an oil bath kettle, heating and refluxing, and carrying out complexation reaction for 12h at 60 ℃; centrifuging the mixture by using a centrifuge after the reaction is finished, taking out a lower precipitate, putting the lower precipitate into a vacuum oven at 70 ℃ for drying for 12 hours, taking out the lower precipitate, and grinding the lower precipitate into powder to obtain a precursor material;
Placing the obtained precursor material into a tube furnace, heating to 900 ℃ at a heating rate of 10 ℃/min under the protection of 80mL/min nitrogen gas flow, and roasting for 2h; cooling to room temperature after roasting; mixing the cooled product with 100mL of sulfuric acid solution with the concentration of 2mol/L, stirring at the stirring speed of 300rpm for 24 hours at room temperature, carrying out acid leaching treatment, and dissolving out a template agent; then filtering and drying for 10 hours at 70 ℃ to obtain the silver-nitrogen doped hierarchical pore carbon material;
the silver-nitrogen doped hierarchical pore carbon material obtained in this example had a silver loading of 1.36wt.%, a nitrogen content of 8.3wt.%, and a specific surface area of 664m 2 Per gram, pore volume of 1.52cm 3 /g (wherein the pore volume ratio of microporous, mesoporous and macroporous structures is 1:2:0.5).
Example 12
Mixing 500mg of basic magnesium carbonate with a loose porous structure, 500mg of polyvinylpyrrolidone and 100mL of methanol, sequentially carrying out ultrasonic treatment at 500W for 30min at normal temperature and stirring at a stirring speed of 300rpm for 6h, centrifuging by a centrifuge, and taking out a lower precipitate to obtain 593mg of matrix material;
uniformly stirring and dispersing the obtained precursor material and 250mL of methanol to obtain a fourth mixed solution; mixing 5mg of silver nitrate and 25mL of methanol for dissolution to obtain a fifth mixed solution; mixing and dissolving 1g of phenanthroline and 25mL of methanol to obtain a sixth mixed solution; dripping the fifth mixed solution and the sixth mixed solution into the fourth mixed solution at a dripping speed of 5mL/min, putting the obtained mixed solution into an oil bath kettle, heating and refluxing, and carrying out complexation reaction for 12h at 60 ℃; centrifuging the mixture by using a centrifuge after the reaction is finished, taking out a lower precipitate, putting the lower precipitate into a vacuum oven at 70 ℃ for drying for 12 hours, taking out the lower precipitate, and grinding the lower precipitate into powder to obtain a precursor material;
Placing the obtained precursor material into a tube furnace, heating to 900 ℃ at a heating rate of 10 ℃/min under the protection of 80mL/min nitrogen gas flow, and roasting for 2h; cooling to room temperature after roasting; mixing the cooled product with 100mL of sulfuric acid solution with the concentration of 2mol/L, stirring at the stirring speed of 300rpm for 24 hours at room temperature, carrying out acid leaching treatment, and dissolving out a template agent; then filtering and drying for 10 hours at 70 ℃ to obtain the silver-nitrogen doped hierarchical pore carbon material;
the silver-nitrogen doped hierarchical pore carbon material obtained in this example had a silver loading of 0.88wt.%, a nitrogen content of 6.3wt.%, and a specific surface area of 592m 2 Per gram, pore volume of 1.77cm 3 /g (wherein the pore volume ratio of microporous, mesoporous and macroporous structures is 1:1:3).
Comparative example 1
Mixing 500mg of massive copper oxide, 500mg of polyvinylpyrrolidone and 100mL of methanol, sequentially carrying out ultrasonic treatment at 500W for 30min at normal temperature, stirring at a stirring speed of 300rpm for 6h, centrifuging by a centrifuge, and taking out a lower precipitate to obtain 668mg of matrix material;
uniformly stirring and dispersing the obtained matrix material and 250mL of methanol to obtain a first mixed solution; mixing 850mg of zinc nitrate hexahydrate, 50mg of nickel nitrate hexahydrate and 25mL of methanol for dissolution to obtain a second mixed solution; 1g of 2-methylimidazole and 25mL of methanol are mixed and dissolved to obtain a third mixed solution; dripping the second mixed solution and the third mixed solution into the first mixed solution at a dripping speed of 5mL/min, putting the obtained mixed solution into an oil bath kettle, heating and refluxing, and carrying out complexation reaction for 12h at 60 ℃; centrifuging the mixture by using a centrifuge after the reaction is finished, taking out a lower precipitate, putting the lower precipitate into a vacuum oven at 70 ℃ for drying for 12 hours, taking out the lower precipitate, and grinding the lower precipitate into powder to obtain a precursor material;
Placing the obtained precursor material into a tube furnace, heating to 900 ℃ at a heating rate of 10 ℃/min under the protection of 80mL/min nitrogen gas flow, and roasting for 2h; cooling to room temperature after roasting; mixing the cooled product with 100mL of sulfuric acid solution with the concentration of 2mol/L, stirring at the stirring speed of 300rpm for 24 hours at room temperature, carrying out acid leaching treatment, and dissolving out a template agent; then filtering and drying for 10 hours at 70 ℃ to obtain a nickel-nitrogen doped massive solid single microporous carbon material;
the nickel-nitrogen doped massive solid single microporous carbon material obtained in this example had a nickel loading of 1.22wt.%, a nitrogen content of 5.6wt.%, and a specific surface area of 617m 2 Per gram, pore volume of 0.31cm 3 /g。
Performance testing
Test example 1
The multistage pore material obtained in example 1 was subjected to scanning transmission electron microscopy, and STEM detection results are shown in fig. 1, and it can be seen from fig. 1 that the multistage pore material obtained in this example has abundant and uniformly dispersed nickel metal single sites.
Test example 2
Scanning electron microscope detection is carried out on the hierarchical pore material obtained in the embodiment 1, the SEM detection result is shown in figure 2, and it can be seen from figure 2 that the hierarchical pore material obtained in the implementation is a micron-sized porous sphere composed of countless layered nano-sheets; and has rich pore channels.
Test example 3
The multistage pore materials obtained in examples 1 to 12 are used as catalysts to catalyze the reduction of carbon dioxide to prepare carbon monoxide, and the specific method comprises the following steps:
mixing 1.2mg of hierarchical pore material, 564 mu L of ethanol and 36 mu L of perfluorinated sulfonic acid type polymer solution with mass concentration of 5% to obtain slurry;
coating the slurry on a surface of 1X 3cm 2 On carbon paper (load of 0.4 mg/cm) 2 ) Obtaining a catalyst electrode (i.e. a working electrode);
the catalyst electrode is used as a cathode, a KOH solution with the concentration of 1mol/L is used as electrolyte, and Ag/AgCl is usedThe electrode (wherein the solvent is KCl solution of 3 mol/L) is used as a reference electrode, the foam nickel is used as a counter electrode, and the anion exchange membrane is used as a diaphragm, so that the gas diffusion electrode is assembled. Setting the water circulation rotating speed to be 30mL/min under the conditions of normal temperature and normal pressure; CO is introduced at a rate of 20mL/min 2 Air flow for 20min to make CO 2 The gas is saturated, cyclic voltammetry scanning is carried out for 30 circles, and the catalyst is activated and the absorbed gas is discharged; after 12min of power on stabilization, 1mL of gas is extracted for gas chromatography detection, H 2 The CO was detected by a Thermal Conductivity Detector (TCD) in the chromatograph, a hydrogen Flame Ionization Detector (FID) equipped with a nickel reformer, and the faraday efficiency and split current density of the product were calculated from the measured product gas content.
Wherein FIG. 4 is a Faraday plot of carbon monoxide for the catalyst of the hierarchical pore material of example 1, and FIG. 5 is a current density plot for the catalyst of the hierarchical pore material of example 1; it can be seen from FIG. 4 that the carbon monoxide Faraday efficiency of Ni-N-C is greater than 90% over a wide voltage window of-0.4 to-1.3V, attaining a maximum of nearly 100% at-0.7V; as can be seen from FIG. 5, the current density of the carbon monoxide component exceeds 100mA cm at-0.6V -2 Reaches a maximum value of 524mA cm at-1.4V -2 ；
The test results are shown in Table 1.
TABLE 1 results of the catalytic carbon dioxide reduction tests for the hierarchical pore materials obtained in examples 1-12
As can be seen from Table 1, the hierarchical porous material obtained by the present invention is used as a catalyst, and can exhibit a larger Faraday efficiency of carbon monoxide at a lower potential and a larger current density in the reaction of preparing carbon monoxide by catalyzing the reduction of carbon dioxide.
Although the foregoing embodiments have been described in some, but not all embodiments of the invention, other embodiments may be obtained according to the present embodiments without departing from the scope of the invention.
Claims (2)
1. The application of the hierarchical pore material in catalyzing carbon dioxide reduction reaction is characterized in that the preparation method of the hierarchical pore material comprises the following steps:
mixing a template agent, a surface modifier and a polar solvent to obtain a matrix material;
growing metal organic compounds on the surface of the matrix material in situ to obtain a precursor material;
sequentially roasting and acid leaching the precursor material to obtain the hierarchical pore material;
the template agent has a loose porous structure; the template agent comprises a metal oxide and/or a metal salt; the metal oxide comprises magnesium oxide and/or zinc oxide; the metal salt comprises basic magnesium carbonate;
the metal organic compound comprises a zeolite imidazole framework or a metal organic complex;
when the metal organic compound is a zeolite imidazole framework, the in-situ growth comprises the steps of: mixing a matrix material, a first soluble metal salt, a second soluble metal salt, 2-methylimidazole and a polar solvent, and carrying out a meridian combination reaction to obtain the precursor material;
the first soluble metal salt is a soluble zinc salt;
the second soluble metal salt comprises one or more of soluble nickel salt, soluble ferric salt, soluble cobalt salt, soluble copper salt, soluble manganese salt, soluble ruthenium salt and soluble silver salt;
When the metal organic compound is a metal organic complex, the in situ growth comprises the steps of:
mixing a matrix material, soluble metal salt, an organic ligand and a polar solvent, and carrying out meridian combination reaction to obtain the precursor material;
the soluble metal salt comprises one or more of soluble nickel salt, soluble ferric salt, soluble cobalt salt, soluble copper salt, soluble manganese salt, soluble ruthenium salt and soluble silver salt;
the organic ligand comprises one or more of phenanthroline, formamide, melamine and polyaniline;
the multistage holes comprise a microporous structure, a mesoporous structure and a macroporous structure; the pore volume ratio of the microporous structure, the mesoporous structure and the macroporous structure is 1: (2-3): (2-3);
the hierarchical pore material is a metal-doped hierarchical pore carbon material, and the mass percentage of the metal is 0.5-15.0%.
2. The use according to claim 1, wherein the baking temperature is 600-1200 ℃ and the holding time is 0.5-10 h.
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