CN114892196A - Hierarchical pore material and preparation method and application thereof - Google Patents
Hierarchical pore material and preparation method and application thereof Download PDFInfo
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- CN114892196A CN114892196A CN202210668347.8A CN202210668347A CN114892196A CN 114892196 A CN114892196 A CN 114892196A CN 202210668347 A CN202210668347 A CN 202210668347A CN 114892196 A CN114892196 A CN 114892196A
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- Prior art keywords
- soluble
- salt
- metal
- mixing
- mixed solution
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- 239000000463 material Substances 0.000 title claims abstract description 81
- 239000002149 hierarchical pore Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 84
- 239000011148 porous material Substances 0.000 claims abstract description 70
- 239000002184 metal Chemical class 0.000 claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 claims abstract description 51
- 239000002798 polar solvent Substances 0.000 claims abstract description 49
- 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 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 150000003839 salts Chemical class 0.000 claims abstract description 43
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 36
- 239000011159 matrix material Substances 0.000 claims abstract description 36
- 239000002253 acid Substances 0.000 claims abstract description 28
- 238000002386 leaching Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 22
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 22
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 18
- 238000011065 in-situ storage Methods 0.000 claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 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
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 6
- 239000003575 carbonaceous material Substances 0.000 claims description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 28
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 18
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 16
- 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
- 229910052759 nickel 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
- 150000003303 ruthenium Chemical class 0.000 claims description 12
- 238000006722 reduction reaction Methods 0.000 claims description 11
- 150000002815 nickel Chemical class 0.000 claims description 10
- 239000013110 organic ligand Substances 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 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
- 239000004793 Polystyrene Substances 0.000 claims description 7
- 150000002505 iron Chemical class 0.000 claims description 7
- 229920002223 polystyrene Polymers 0.000 claims description 7
- 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
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 239000003446 ligand Substances 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
- 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 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 239000005416 organic matter Substances 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 18
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 17
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 159
- 239000011259 mixed solution Substances 0.000 description 105
- 238000003756 stirring Methods 0.000 description 72
- 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 35
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 28
- 239000000047 product Substances 0.000 description 24
- 239000000243 solution Substances 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- 238000004321 preservation Methods 0.000 description 15
- 238000010992 reflux Methods 0.000 description 15
- 239000000126 substance Substances 0.000 description 14
- 229910001873 dinitrogen Inorganic materials 0.000 description 13
- 238000011068 loading method Methods 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
- 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
- 239000007789 gas Substances 0.000 description 10
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-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
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000010668 complexation reaction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000012445 acidic reagent Substances 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 238000001514 detection method Methods 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
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-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
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-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
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 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
- 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
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 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
- 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
- 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
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 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
- 229910021591 Copper(I) chloride Inorganic materials 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
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- XIELUSWGOAVQLB-UHFFFAOYSA-N [N].[Ag] Chemical compound [N].[Ag] XIELUSWGOAVQLB-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
- 230000003213 activating effect Effects 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
- 230000015572 biosynthetic process 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
- 230000000536 complexating effect Effects 0.000 description 2
- RFKZUAOAYVHBOY-UHFFFAOYSA-M copper(1+);acetate Chemical compound [Cu+].CC([O-])=O RFKZUAOAYVHBOY-UHFFFAOYSA-M 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 2
- WIVXEZIMDUGYRW-UHFFFAOYSA-L copper(i) sulfate Chemical compound [Cu+].[Cu+].[O-]S([O-])(=O)=O WIVXEZIMDUGYRW-UHFFFAOYSA-L 0.000 description 2
- 229940076286 cupric acetate Drugs 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- 229940045803 cuprous chloride Drugs 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000007599 discharging 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
- 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
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 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
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 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
- 239000007788 liquid Substances 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
- 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
- 239000000203 mixture Substances 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
- FZHCFNGSGGGXEH-UHFFFAOYSA-N ruthenocene Chemical compound [Ru+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 FZHCFNGSGGGXEH-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 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
- 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
- CMPNPRUFRJFQIB-UHFFFAOYSA-N [N].[Cu] Chemical compound [N].[Cu] CMPNPRUFRJFQIB-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
- YDVGDXLABZAVCP-UHFFFAOYSA-N azanylidynecobalt Chemical compound [N].[Co] YDVGDXLABZAVCP-UHFFFAOYSA-N 0.000 description 1
- YYXHRUSBEPGBCD-UHFFFAOYSA-N azanylidyneiron Chemical compound [N].[Fe] YYXHRUSBEPGBCD-UHFFFAOYSA-N 0.000 description 1
- RBVYPNHAAJQXIW-UHFFFAOYSA-N azanylidynemanganese Chemical compound [N].[Mn] RBVYPNHAAJQXIW-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission 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
- 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
- YRXSBLDMEFVORK-UHFFFAOYSA-N dimethyl(tritriacontan-17-yl)azanium bromide Chemical compound [Br-].C(CCCCCCCCCCCCCCC)C([NH+](C)C)CCCCCCCCCCCCCCCC YRXSBLDMEFVORK-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 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
- 238000010304 firing Methods 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
- 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 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
- BAOGIWGDRNSXGA-UHFFFAOYSA-N propan-2-one;zinc Chemical compound [Zn].CC(C)=O BAOGIWGDRNSXGA-UHFFFAOYSA-N 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000000630 rising effect Effects 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
- 239000007858 starting material Substances 0.000 description 1
- 238000010792 warming Methods 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
Images
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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
- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- 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
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- C25B3/00—Electrolytic production of organic compounds
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- C25B3/00—Electrolytic production of organic compounds
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- C25B3/07—Oxygen containing compounds
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- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
- C25B3/26—Reduction of carbon dioxide
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Abstract
The invention belongs to the technical field of carbon dioxide reduction, and particularly relates to a hierarchical pore material, and 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 a metal organic compound 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 porous material; the template 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 partial current 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 pore material, and a preparation method and application thereof.
Background
The combustion of fossil fuels causes excessive emissions of carbon dioxide, accelerating global warming, resulting in rising sea levels and a series of extreme weather occurrences. Therefore, it is imperative to convert carbon dioxide to valuable carbon products.
Among the existing carbon dioxide conversion technologies, the carbon dioxide electrochemical reduction technology has the advantages of mild reaction conditions, easy reaction control and easy modularization. The products of the electrochemical reduction of carbon dioxide mainly comprise 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 also be used as a chemical raw material to directly participate in industrial synthesis.
The catalyst for preparing carbon monoxide by carbon dioxide electrochemical reduction mainly comprises a silver alloy catalyst, a carbon nano tube loaded metal composite catalyst and the like, but the activity of the existing catalyst is low, so that the defects of low pull-to-first efficiency and low current density of a carbon monoxide method in the carbon dioxide electrochemical reduction process are caused.
Disclosure of Invention
The invention aims to provide a hierarchical porous material, a preparation method and application thereof.
In order to achieve the above purpose, the invention provides the following technical scheme:
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 a metal organic compound 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 porous material;
the template 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 zeolitic imidazole framework or a metal organic complex.
Preferably, when the metal organic compound is a zeolitic imidazole framework, the in situ growth comprises the steps of: mixing the base material, the first soluble metal salt, the second soluble metal salt, 2-methylimidazole and a polar solvent, and carrying out a 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 iron 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 following steps:
mixing a base material, soluble metal salt, an organic ligand and a polar solvent, and carrying out a complex 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 matter 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 by polystyrene;
when the template agent is polystyrene, the preparation method of the hierarchical porous material does not comprise acid leaching treatment.
The invention also provides the hierarchical porous material prepared by the preparation method in the technical scheme, and the hierarchical porous material is a metal-doped hierarchical porous 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 the technical scheme 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 a metal organic compound 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 porous material; the template has a loose porous structure; the template agent comprises one or more of metal oxide, metal salt and silicon oxide. According to the invention, a metal organic compound grows in situ on the surface of a template agent with a loose porous structure, after roasting and acid leaching, the metal organic compound can form a hierarchical porous structure similar to the template agent in shape, and meanwhile, after roasting and acid leaching, the loose porous structure of the template agent can be transferred to a carbon material, and finally the metal-doped carbon material with the hierarchical porous structure is formed; when the obtained hierarchical porous 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 partial current density of the carbon monoxide are improved.
Drawings
FIG. 1 is a STEM of a hierarchical pore material obtained in example 1;
FIG. 2 is an SEM photograph of the hierarchical porous material obtained in example 1;
FIG. 3 is a schematic synthesis scheme of example 1;
FIG. 4 is a graph showing the Faraday efficiency of carbon monoxide in the production of carbon monoxide by the reduction of carbon dioxide using the hierarchical porous material obtained in example 1 as a catalyst;
FIG. 5 is a graph of the partial current density in the preparation of carbon monoxide by the reduction of carbon dioxide using the hierarchical porous 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 a metal organic compound 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 porous material;
the template 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 starting materials for the preparation are commercially available products known to those skilled in the art unless otherwise specified.
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 loose porous structure. In the invention, the template comprises one or more of metal oxide, metal salt and silicon oxide. 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 agent is two or more selected from the above-mentioned choices, the present invention does not specifically limit the ratio of the specific substance, and the specific substance may be mixed in any ratio.
In the invention, the surface modifier preferably comprises one or more of polyvinylpyrrolidone, dodecyl trimethyl ammonium bromide, dicetyl trimethyl ammonium bromide and sodium dodecyl sulfonate; when the surface modifier is two or more selected from the above-mentioned options, the specific substance may be mixed at any ratio without any particular limitation.
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 selected from the above-mentioned solvents, the specific material may be mixed in any ratio without any particular limitation.
In the present invention, the mass ratio of the surface modifier to the templating agent is preferably 1: 10-10: 1, more preferably 1: 9-9: 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 45 mg: 1mL, more preferably 10-40 mg: 1 mL.
In the present invention, the mixing is preferably performed at room temperature. In the present invention, the mixing preferably includes sequentially performing the ultrasonic treatment and the stirring. In the invention, the power of the ultrasonic wave is preferably 200-3000W, more preferably 500-2500W, and more preferably 1000-2000W; the time is preferably 30 min. In the invention, the rotation speed of the stirring is preferably 100-10000 rpm, more preferably 500-9000 rpm, and more preferably 1000-8000 rpm; the time is preferably 6 h. After said mixing is complete, the present invention also preferably comprises centrifuging the resulting mixture. The present invention does not require any particular procedure for the separation and centrifugation, and can be carried out by procedures well known to those skilled in the art.
After the matrix material is obtained, the metal organic compound grows on the surface of the matrix material in situ to obtain the precursor material.
In the present invention, the metal organic compound preferably has a loose porous structure.
In the present invention, the metal organic compound preferably comprises a zeolitic imidazole framework or a metal organic complex.
In the present invention, when the metal-organic compound is a zeolitic imidazole framework, the in situ growth preferably comprises the steps of: and mixing the base material, the first soluble metal salt, the second soluble metal salt, the 2-methylimidazole and the polar solvent, and carrying out a complex reaction to obtain the 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 acetone and zinc acetate; when the soluble zinc salt is two or more selected from the above-mentioned materials, the ratio of the specific material is not particularly limited in the present invention, and the soluble zinc salt may be mixed in any ratio. In a particular embodiment of the invention, the zinc nitrate is preferably added in the form of zinc nitrate hexahydrate.
In the invention, the second soluble metal salt preferably 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 second soluble metal salt is two or more selected from the above-mentioned groups, the specific material may be mixed at any ratio without any particular limitation.
In the invention, the soluble nickel salt preferably comprises one or more of nickel nitrate, nickel citrate, nickel acetate, nickel sulfate and nickel chloride; when the soluble nickel salt is two or more selected from the above-mentioned groups, the specific material may be mixed at any ratio without any particular limitation. In a particular embodiment of the invention, the nickel nitrate is preferably added in the form of nickel nitrate hexahydrate.
In the invention, the soluble ferric salt preferably comprises 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 selected from the above-mentioned options, the ratio of the specific substance in the present invention is not particularly limited, and the soluble iron salt may be mixed in any ratio. In a particular embodiment of the invention, the iron nitrate is preferably added in the form of iron nitrate nonahydrate.
In the invention, the soluble cobalt salt preferably comprises one or more of cobalt nitrate, cobalt citrate, cobalt acetate, cobalt sulfate and cobalt chloride; when the soluble cobalt salt is two or more selected from the above specific choices, the specific material ratio is not particularly limited in the present invention, and the soluble cobalt salt may be mixed at any ratio. In a particular embodiment of the invention, the cobalt nitrate is preferably added in the form of cobalt nitrate hexahydrate.
In the invention, the soluble copper salt preferably comprises one or more of cupric nitrate, cupric acetate, cupric sulfate, cupric chloride, cuprous acetate, cuprous nitrate, cuprous sulfate and cuprous chloride; when the soluble copper salt is two or more selected from the above specific choices, the present invention does not specifically limit the ratio of the specific substances, 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 invention, the soluble manganese salt preferably comprises one or more of manganese nitrate, manganese citrate, manganese acetate, manganese sulfate and manganese chloride; when the soluble manganese salt is two or more selected from the above specific choices, the present invention does not specifically limit the proportion of the specific substance, and the soluble manganese salt may be mixed in any proportion. In the present invention, the manganese nitrate is preferably added in the form of manganese nitrate hexahydrate.
In the invention, the soluble ruthenium salt preferably comprises one or more of ruthenium chloride, ruthenium acetate and ruthenocene; when the soluble ruthenium salt is two or more selected from the above specific choices, the present invention does not specifically limit the proportion of the specific substances, and the soluble ruthenium salt may be mixed in any proportion. In the present invention, the soluble silver salt preferably comprises 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 specific material may be mixed at any ratio without any particular limitation.
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, more 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 50 mg: 1mL, more preferably 5 to 45 mg: 1mL, more preferably 10-40 mg: 1 mL.
The mixing process is not particularly limited in the present invention, and may be performed by a process known to those skilled in the art.
In a specific embodiment of the present invention, the mixing process preferably comprises: firstly mixing a base material and a first polar solvent to obtain a first mixed solution; secondly 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 and a third polar solvent to obtain a third mixed solution; and dropping 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 the above-defined types of polar solvents, and are not described herein 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 solution.
In the invention, the dosage ratio of the matrix material to the first polar solvent is preferably 0.5-100 mg: 1mL, more preferably 20-80 mg: 1 mL. In the present invention, the ratio of the first soluble metal salt to the second polar solvent is preferably 0.5 to 100 mg: 1mL, more preferably 20-50 mg: 1 mL. In the invention, the dosage ratio of the 2-methylimidazole to the third polar solvent is preferably 0.5-100 mg: 1mL, more preferably 20-50 mg: 1 mL.
The process of the first mixing, the second mixing and the third mixing is not particularly limited, and may be performed by a process known to those skilled in the art.
In the present invention, the second mixed solution and the third mixed solution are dropped at respective rates of preferably 2 to 10mL/min, and more preferably 5 mL/min.
In the invention, the temperature of the complexation reaction is preferably 20-200 ℃, more preferably 40-180 ℃, and more preferably 60-160 ℃; the time is preferably 6 to 48 hours, more preferably 10 to 40 hours, and even more preferably 15 to 35 hours. In the present invention, the complexation reaction is preferably performed under stirring conditions; the rotation speed of the stirring is preferably 100-10000 rpm, more preferably 300-9000 rpm, and even more preferably 800-8000 rpm. In the present invention, the complexation reaction is preferably performed under reflux conditions.
After the completion of the complexing reaction, the present invention also preferably comprises subjecting the resulting product to centrifugation, drying and grinding. The process of centrifugation and grinding is not particularly limited in the present invention, and may be performed by a process known to those skilled in the art. In the present invention, the temperature of the drying is preferably 70 ℃; the time is preferably 12 h. 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 base material, soluble metal salt, an organic ligand and a polar solvent, and carrying out a complex reaction to obtain the precursor material.
In the present invention, the soluble metal salt preferably includes one or more of soluble nickel salt, soluble iron salt, soluble cobalt salt, soluble copper salt, soluble manganese salt, soluble ruthenium salt and soluble silver salt.
In the invention, the soluble nickel salt preferably comprises one or more of nickel nitrate, nickel citrate, nickel acetate, nickel sulfate and nickel chloride; when the soluble nickel salt is two or more selected from the above-mentioned groups, the specific material may be mixed at any ratio without any particular limitation. In a particular embodiment of the invention, the nickel nitrate is preferably added in the form of nickel nitrate hexahydrate.
In the invention, the soluble ferric salt preferably comprises 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 selected from the above-mentioned options, the ratio of the specific substance in the present invention is not particularly limited, and the soluble iron salt may be mixed in any ratio. In a particular embodiment of the invention, the iron nitrate is preferably added in the form of iron nitrate nonahydrate.
In the invention, the soluble cobalt salt preferably comprises one or more of cobalt nitrate, cobalt citrate, cobalt acetate, cobalt sulfate and cobalt chloride; when the soluble cobalt salt is two or more selected from the above specific choices, the specific material ratio is not particularly limited in the present invention, and the soluble cobalt salt may be mixed at any ratio. In a particular embodiment of the invention, the cobalt nitrate is preferably added in the form of cobalt nitrate hexahydrate.
In the invention, the soluble copper salt preferably comprises one or more of cupric nitrate, cupric acetate, cupric sulfate, cupric chloride, cuprous acetate, cuprous nitrate, cuprous sulfate and cuprous chloride; when the soluble copper salt is two or more selected from the above specific choices, the present invention does not specifically limit the ratio of the specific substances, 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 invention, the soluble manganese salt preferably comprises one or more of manganese nitrate, manganese citrate, manganese acetate, manganese sulfate and manganese chloride; when the soluble manganese salt is two or more selected from the above specific choices, the present invention does not specifically limit the proportion of the specific substance, and the soluble manganese salt may be mixed in any proportion. In the present invention, the manganese nitrate is preferably added in the form of manganese nitrate hexahydrate.
In the invention, the soluble ruthenium salt preferably comprises one or more of ruthenium chloride, ruthenium acetate and ruthenocene; when the soluble ruthenium salt is two or more selected from the above specific choices, the present invention does not specifically limit the ratio of the specific substances, and the soluble ruthenium salt may be mixed in any ratio. In the present invention, the soluble silver salt preferably comprises silver nitrate.
In the invention, the organic ligand preferably comprises one or more of phenanthroline, formamide, melamine and polyaniline; when the organic ligands are two or more selected from the above-mentioned groups, the specific ratio of the organic ligands is not particularly limited, and the organic ligands may be mixed at 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 specific material may be mixed at any ratio without any particular limitation.
In the present invention, the mass ratio of the soluble metal salt to the organic ligand is preferably 1: 50-50: 1, more preferably 1: 30-30: 1, more preferably 1: 20-20: 1. in the invention, the dosage ratio of the soluble metal salt to the polar solvent is preferably 0.5-500 mg: 1mL, more preferably 10 to 450 mg: 1mL, more preferably 50-400 mg: 1 mL.
The mixing process is not particularly limited in the present invention, and may be performed by a process known to those skilled in the art.
In a specific embodiment of the present invention, the mixing process preferably comprises: fourthly, mixing the base material and a fourth polar solvent to obtain a fourth mixed solution; fifthly, mixing the soluble metal salt and a fifth polar solvent to obtain a fifth mixed solution; sixthly, mixing the organic matter ligand and a sixth polar solvent to obtain a sixth mixed solution; and dropping the fifth mixed solution and the sixth mixed solution into the fourth mixed solution.
In the present invention, the kinds of the fourth polar solvent, the fifth polar solvent and the sixth polar solvent are the same as the kinds of the above-defined polar solvents, and are not described herein again.
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 technical solution.
In the invention, the dosage ratio of the base material to the fourth polar solvent is preferably 0.5-100 mg: 1mL, more preferably 10 to 80 mg: 1 mL. In the invention, the dosage ratio of the soluble metal salt to the fifth polar solvent is preferably 0.5-100 mg: 1mL, more preferably 10 to 80 mg: 1 mL. In the invention, the dosage ratio of the organic ligand to the sixth polar solvent is preferably 0.5-100 mg: 1mL, more preferably 10 to 80 mg: 1 mL.
The process of the fourth mixing, the fifth mixing and the sixth mixing is not particularly limited, and may be performed by a process known to those skilled in the art.
In the present invention, the dropping speed of the fifth mixed liquid and the sixth mixed liquid is preferably 2 to 10mL/min, and more preferably 5mL/min independently.
In the invention, the temperature of the complexation reaction is preferably 20-200 ℃, more preferably 40-180 ℃, and more preferably 60-160 ℃; the time is preferably 6 to 48 hours, more preferably 10 to 40 hours, and even more preferably 15 to 35 hours. In the present invention, the complexation reaction is preferably performed under stirring conditions; the rotation speed of the stirring is preferably 100-10000 rpm, more preferably 300-9000 rpm, and even more preferably 800-8000 rpm. In the present invention, the complexation reaction is preferably performed under reflux conditions.
After the completion of the complexing reaction, the present invention also preferably comprises subjecting the resulting product to centrifugation, drying and grinding. The process of centrifugation and grinding is not particularly limited in the present invention, and may be performed by a process known to those skilled in the art. In the present invention, the temperature of the drying is preferably 70 ℃; the time is preferably 12 h. In the present invention, the drying is preferably performed in a vacuum oven.
After the precursor material is obtained, the invention carries out roasting and acid leaching treatment on the precursor material to obtain the hierarchical porous material.
In the invention, the roasting temperature is preferably 600-1200 ℃, more preferably 700-1100 ℃, and more preferably 800-1000 ℃; the heating rate for heating to the roasting temperature is preferably 10 ℃/min; the heat preservation time is preferably 0.5-10 h, more preferably 1-9 h, and even more preferably 2-8 h. In the present invention, the calcination is preferably carried out 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 selected from the above-mentioned options, the proportion of the specific substance in the present invention is not particularly limited, and the specific substance may be mixed in any proportion. In the present invention, the introduction rate of the protective atmosphere is preferably 80 mL/min. In the present invention, the calcination is preferably carried out 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 those skilled in the art can use the same.
In the invention, the acid reagent adopted 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 selected from the above-mentioned groups, the specific substance may be mixed at any ratio without any particular limitation in the present invention.
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, and more preferably 2 mol/L. In the present invention, the amount of the acidic reagent is not particularly limited, and the template may be removed.
In the present invention, the acid leaching treatment is preferably performed under stirring; the rotation speed of the stirring is preferably 100-10000 rpm, more preferably 300-9000 rpm, and even more preferably 800-8000 rpm; the time is preferably 24 h. In the present invention, the template agent can be removed by acid leaching treatment.
After the acid leaching treatment is completed, the invention also preferably comprises filtering and drying the obtained product.
The filtration process is not particularly limited in the present invention, and may be performed by a process known to those skilled in the art. In the present invention, the drying temperature is preferably 70 ℃ and the drying time is preferably 10 hours.
As another embodiment of the present invention, the templating agent is replaced with polystyrene. In the invention, when the template agent is polystyrene, the preparation method of the hierarchical porous material does not comprise acid leaching treatment. In the present invention, when the template is polystyrene, it is preferable to remove the template during firing.
The invention also provides the hierarchical porous material prepared by the preparation method in the technical scheme, and the hierarchical porous material is a metal-doped hierarchical porous 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 nanoporous carbon material also preferably comprises 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 even more preferably 7.0 to 13.0% by mass.
In the present invention, the metal (M) on the hierarchical porous carbon material is preferably M-N 4 In the form of single sites.
In the invention, the electronic structure of the hierarchical porous material can be adjusted by doping the hierarchical porous material with metal and nitrogen elements, and the catalytic activity of the hierarchical porous material is improved from the thermodynamic aspect; the reaction kinetics in the carbon dioxide conversion process can be further promoted by combining the arrangement of the multi-stage pore structure, and the Faraday efficiency and the current distribution density of the carbon monoxide are improved.
In the invention, the specific surface area of the hierarchical porous material is preferably 500-2000 m 2 (ii) g, more preferably 600 to 1900m 2 A concentration of 700 to 1800m is more preferable 2 (ii)/g; the pore volume is preferably 0.2-2 cm 3 A more preferable range is 0.5 to 1.5 cm/g 3 A concentration of 0.8 to 1.2cm 3 (ii) in terms of/g. In the present invention, the hierarchical 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), and more preferably 1: (2-3): (2-3).
The invention also provides application of the hierarchical porous material in the technical scheme in catalyzing carbon dioxide reduction reaction.
In the present invention, the application preferably comprises the steps of:
mixing the hierarchical porous material, ethanol and a perfluorosulfonic acid polymer solution to obtain slurry; the mass concentration of the perfluorosulfonic acid polymer solution is preferably 5%; the dosage ratio of the hierarchical porous material, ethanol and the perfluorosulfonic acid type polymer solution is preferably 1.2 mg: 564 μ L: 36 mu L of the solution;
coating the slurry on a 1 × 3cm substrate 2 On carbon paper (load amount is 0.4 mg/cm) 2 ) Obtaining a catalyst electrode (namely a working electrode);
the catalyst electrode is used as a cathode, a 1mol/L KOH solution is used as an electrolyte, an Ag/AgCl electrode (the solvent of the Ag/AgCl electrode is a 3mol/L KCl solution) is used as a reference electrode, and foamed nickel is used as a counter electrodeAnd the anion exchange membrane is taken as a diaphragm to assemble the gas diffusion electrode. Under the conditions of normal temperature and normal pressure, setting the water circulation rotation speed to be 30 mL/min; CO was introduced at a rate of 20mL/min 2 Flowing for 20min to make CO 2 When the gas is saturated, performing cyclic voltammetry scanning for 30 circles, activating the catalyst and simultaneously discharging the absorbed gas; electrifying for 12min, extracting 1mL of gas for gas chromatography detection, and H 2 The Faraday efficiency and the fractional current density of the product were calculated from the measured gas content of the product, which was detected by a Thermal Conductivity Detector (TCD) in the chromatograph, CO by a hydrogen Flame Ionization Detector (FID) equipped with a nickel reformer.
For further illustration of the present invention, the following detailed description of a hierarchical pore material and its preparation method and application are provided in conjunction with 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 stirring for 30min at the power of 500W at normal temperature and at the stirring speed of 300rpm for 6h, centrifuging by using a centrifuge, and taking out a lower-layer precipitate to obtain 621mg of a matrix material;
uniformly stirring and dispersing the obtained matrix material and 250mL of methanol to obtain a first mixed solution; mixing and dissolving 850mg of zinc nitrate hexahydrate, 50mg of nickel nitrate hexahydrate and 25mL of methanol to obtain a second mixed solution; mixing and dissolving 1g of 2-methylimidazole and 25mL of methanol to obtain a third mixed solution; dropwise adding the second mixed solution and the third mixed solution into the first mixed solution at a dropwise adding speed of 5mL/min, putting the obtained mixed solution into an oil bath pot, heating and refluxing, and carrying out a complex reaction for 12 hours at a temperature of 60 ℃; centrifuging by using a centrifuge after the reaction is finished, taking out the lower-layer precipitate, putting the precipitate into a vacuum oven at 70 ℃ for drying for 12h, taking out the precipitate, and grinding the precipitate into powder to obtain a precursor material;
placing the obtained precursor material in a tube furnace, heating to 900 ℃ at a heating rate of 10 ℃/min under the protection of 80mL/min nitrogen gas flow, and then roasting, wherein the heat preservation time is 2 h; 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 for acid leaching treatment, and dissolving out a template agent; then drying for 10h at 70 ℃ after filtering to obtain the nickel-nitrogen doped hierarchical pore carbon material;
the synthetic route of this example is schematically shown in FIG. 3;
the loading amount of nickel in the nickel-nitrogen doped hierarchical porous carbon material obtained in the example is 1.8 wt.%, the nitrogen content is 7.8 wt.%, and the specific surface area is 672m 2 Per g, pore volume 1.49cm 3 (wherein the pore volume ratio of the microporous structure, the mesoporous structure and the macroporous structure 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 stirring for 30min at the power of 500W at normal temperature and at the stirring speed of 300rpm for 6h, centrifuging by using a centrifuge, and taking out a lower-layer precipitate to obtain 634mg of a base material;
uniformly stirring and dispersing the obtained matrix material and 250mL of methanol to obtain a first mixed solution; mixing and dissolving 850mg of zinc nitrate hexahydrate, 50mg of nickel nitrate hexahydrate and 25mL of methanol to obtain a second mixed solution; mixing and dissolving 1g of 2-methylimidazole and 25mL of methanol to obtain a third mixed solution; dropwise adding the second mixed solution and the third mixed solution into the first mixed solution at a dropwise adding speed of 5mL/min, putting the obtained mixed solution into an oil bath pot, heating and refluxing, and carrying out a complex reaction for 12 hours at a temperature of 60 ℃; centrifuging by using a centrifuge after the reaction is finished, taking out the lower-layer precipitate, putting the precipitate into a vacuum oven at 70 ℃ for drying for 12h, taking out the precipitate, and grinding the precipitate into powder to obtain a precursor material;
placing the obtained precursor material in a tube furnace, heating to 900 ℃ at a heating rate of 10 ℃/min under the protection of 80mL/min nitrogen gas flow, and then roasting, wherein the heat preservation time is 2 h; 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 for acid leaching treatment, and dissolving out a template agent; then drying for 10h at 70 ℃ after filtering to obtain the nickel-nitrogen doped hierarchical pore carbon material;
the loading amount of nickel in the nickel-nitrogen doped hierarchical porous carbon material obtained in the example is 1.7 wt.%, the nitrogen content is 7.5 wt.%, and the specific surface area is 654m 2 Per g, pore volume 1.46cm 3 (wherein the pore volume ratio of the microporous structure, the mesoporous structure and the macroporous structure 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 stirring for 30min at the power of 500W at normal temperature and at the stirring speed of 300rpm for 6h, centrifuging by using a centrifuge, and taking out a lower-layer precipitate to obtain a matrix material of 586 mg;
uniformly stirring and dispersing the obtained matrix material and 250mL of methanol to obtain a first mixed solution; mixing and dissolving 850mg of zinc nitrate hexahydrate, 50mg of nickel nitrate hexahydrate and 25mL of methanol to obtain a second mixed solution; mixing and dissolving 1g of 2-methylimidazole and 25mL of methanol to obtain a third mixed solution; dropwise adding the second mixed solution and the third mixed solution into the first mixed solution at a dropwise adding speed of 5mL/min, putting the obtained mixed solution into an oil bath pot, heating and refluxing, and carrying out a complex reaction for 12 hours at a temperature of 60 ℃; centrifuging by using a centrifuge after the reaction is finished, taking out the lower-layer precipitate, putting the precipitate into a vacuum oven at 70 ℃ for drying for 12h, taking out the precipitate, and grinding the precipitate into powder to obtain a precursor material;
placing the obtained precursor material in a tube furnace, heating to 900 ℃ at a heating rate of 10 ℃/min under the protection of 80mL/min nitrogen gas flow, and then roasting, wherein the heat preservation time is 2 h; 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 for acid leaching treatment, and dissolving out a template agent; then drying for 10h at 70 ℃ after filtering to obtain the nickel-nitrogen doped hierarchical pore carbon material;
the loading of nickel in the nickel-nitrogen doped hierarchical porous carbon material obtained in the example is 1.7 wt.%, the nitrogen content is 7.2 wt.%, and the specific surface area is 658m 2 Per g, pore volume 1.37cm 3 (wherein the pore volume ratio of the microporous structure, the mesoporous structure and the macroporous structure 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 stirring for 30min at the power of 500W at normal temperature and at the stirring speed of 300rpm for 6h, centrifuging by using a centrifuge, and taking out a lower-layer 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; mixing and dissolving 1g of 2-methylimidazole and 25mLN, N-dimethylformamide to obtain a third mixed solution; dropwise adding the second mixed solution and the third mixed solution into the first mixed solution at a dropwise adding speed of 5mL/min, putting the obtained mixed solution into an oil bath pot, heating and refluxing, and carrying out a complex reaction for 12 hours at 120 ℃; centrifuging by using a centrifuge after the reaction is finished, taking out the lower-layer precipitate, putting the precipitate into a vacuum oven at 70 ℃ for drying for 12h, taking out the precipitate, and grinding the precipitate into powder to obtain a precursor material;
placing the obtained precursor material in a tube furnace, heating to 900 ℃ at a heating rate of 10 ℃/min under the protection of 80mL/min nitrogen gas flow, and then roasting, wherein the heat preservation time is 2 h; 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 for acid leaching treatment, and dissolving out a template agent; then drying for 10h at 70 ℃ after filtering to obtain the nickel-nitrogen doped hierarchical pore carbon material;
the loading of nickel in the nickel-nitrogen doped hierarchical porous carbon material obtained in the example was 1.2 wt.%, the nitrogen content was 6.9 wt.%, and the specific surface area was 608m 2 Per g, pore volume 1.35cm 3 (wherein the pore volume ratio of the microporous structure, the mesoporous structure and the macroporous structure 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 stirring for 30min at the power of 500W at normal temperature and at the stirring speed of 300rpm for 6h, centrifuging by using a centrifuge, and taking out a lower-layer precipitate to obtain 618mg of a matrix material;
uniformly stirring and dispersing the obtained precursor material and 250mL of methanol to obtain a fourth mixed solution; mixing and dissolving 50mg of nickel nitrate hexahydrate and 25mL of methanol to obtain a fifth mixed solution; mixing and dissolving 1g of phenanthroline and 25mL of methanol to obtain a sixth mixed solution; dropwise adding the fifth mixed solution and the sixth mixed solution into the fourth mixed solution at a dropwise adding speed of 5mL/min, putting the obtained mixed solution into an oil bath pot, heating and refluxing, and carrying out a complex reaction for 12 hours at a temperature of 60 ℃; centrifuging by using a centrifuge after the reaction is finished, taking out the lower-layer precipitate, putting the precipitate into a vacuum oven at 70 ℃ for drying for 12h, taking out the precipitate, and grinding the precipitate into powder to obtain a precursor material;
placing the obtained precursor material in a tube furnace, heating to 900 ℃ at a heating rate of 10 ℃/min under the protection of 80mL/min nitrogen gas flow, and then roasting, wherein the heat preservation time is 2 h; 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 drying for 10h at 70 ℃ after filtering to obtain the nickel-nitrogen doped hierarchical pore carbon material;
the loading of nickel in the nickel-nitrogen doped hierarchical porous carbon material obtained in the example was 1.2 wt.%, the nitrogen content was 7.1 wt.%, and the specific surface area was 629m 2 Per g, pore volume 1.68cm 3 (wherein the pore volume ratio of the microporous structure, the mesoporous structure and the macroporous structure 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 stirring for 30min at the power of 500W at normal temperature and at the stirring speed of 300rpm for 6h, centrifuging by using a centrifuge, and taking out a lower-layer precipitate to obtain 615mg of a matrix material;
uniformly stirring and dispersing the obtained matrix material and 250mL of methanol to obtain a first mixed solution; mixing and dissolving 850mg of zinc nitrate hexahydrate, 50mg of ferric nitrate nonahydrate and 25mL of methanol to obtain a second mixed solution; mixing and dissolving 1g of 2-methylimidazole and 25mL of methanol to obtain a third mixed solution; dropwise adding the second mixed solution and the third mixed solution into the first mixed solution at a dropwise adding speed of 5mL/min, putting the obtained mixed solution into an oil bath pot, heating and refluxing, and carrying out a complex reaction for 12 hours at a temperature of 60 ℃; centrifuging by using a centrifuge after the reaction is finished, taking out the lower-layer precipitate, putting the precipitate into a vacuum oven at 70 ℃ for drying for 12h, taking out the precipitate, and grinding the precipitate into powder to obtain a precursor material;
placing the obtained precursor material in a tube furnace, heating to 900 ℃ at a heating rate of 10 ℃/min under the protection of 80mL/min nitrogen gas flow, and then roasting, wherein the heat preservation time is 2 h; 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 for acid leaching treatment, and dissolving out a template agent; then drying for 10h at 70 ℃ after filtering to obtain the iron-nitrogen doped hierarchical pore carbon material;
the iron-nitrogen-doped hierarchical porous carbon material obtained in the example had an iron loading of 1.82 wt.%, a nitrogen content of 7.7 wt.%, and a specific surface area of 696m 2 Per g, pore volume 1.79cm 3 (wherein the pore volume ratio of the microporous structure, the mesoporous structure and the macroporous structure 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 stirring for 30min at the power of 500W at normal temperature and at the stirring speed of 300rpm for 6h, centrifuging by using a centrifuge, and taking out a lower-layer precipitate to obtain 609mg of a matrix material;
uniformly stirring and dispersing the obtained matrix material and 250mL of methanol to obtain a first mixed solution; mixing and dissolving 850mg of zinc nitrate hexahydrate, 50mg of cobalt nitrate hexahydrate and 25mL of methanol to obtain a second mixed solution; mixing and dissolving 1g of 2-methylimidazole and 25mL of methanol to obtain a third mixed solution; dropwise adding the second mixed solution and the third mixed solution into the first mixed solution at a dropwise adding speed of 5mL/min, putting the obtained mixed solution into an oil bath pot, heating and refluxing, and carrying out a complex reaction for 12 hours at a temperature of 60 ℃; centrifuging by using a centrifuge after the reaction is finished, taking out the lower-layer precipitate, putting the precipitate into a vacuum oven at 70 ℃ for drying for 12h, taking out the precipitate, and grinding the precipitate into powder to obtain a precursor material;
placing the obtained precursor material in a tube furnace, heating to 900 ℃ at a heating rate of 10 ℃/min under the protection of 80mL/min nitrogen gas flow, and then roasting, wherein the heat preservation time is 2 h; 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 for acid leaching treatment, and dissolving out a template agent; then drying for 10h at 70 ℃ after filtering to obtain a cobalt-nitrogen doped hierarchical pore carbon material;
the cobalt-nitrogen-doped hierarchical porous carbon material obtained in the example had a cobalt loading of 1.08 wt.%, a nitrogen content of 8.6 wt.%, and a specific surface area of 702m 2 Per g, pore volume 1.82cm 3 (wherein the pore volume ratio of the microporous structure, the mesoporous structure and the macroporous structure 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 stirring for 30min at the power of 500W at normal temperature and at the stirring speed of 300rpm for 6h, centrifuging by using a centrifuge, and taking out a lower-layer precipitate to obtain 616mg of a matrix material;
uniformly stirring and dispersing the obtained matrix material and 250mL of methanol to obtain a first mixed solution; mixing and dissolving 850mg of zinc nitrate hexahydrate, 50mg of copper nitrate hexahydrate and 25mL of methanol to obtain a second mixed solution; mixing and dissolving 1g of 2-methylimidazole and 25mL of methanol to obtain a third mixed solution; dropwise adding the second mixed solution and the third mixed solution into the first mixed solution at a dropwise adding speed of 5mL/min, putting the obtained mixed solution into an oil bath pot, heating and refluxing, and carrying out a complex reaction for 12 hours at a temperature of 60 ℃; centrifuging by using a centrifuge after the reaction is finished, taking out the lower-layer precipitate, putting the precipitate into a vacuum oven at 70 ℃ for drying for 12h, taking out the precipitate, and grinding the precipitate into powder to obtain a precursor material;
placing the obtained precursor material in a tube furnace, heating to 900 ℃ at a heating rate of 10 ℃/min under the protection of 80mL/min nitrogen gas flow, and then roasting, wherein the heat preservation time is 2 h; 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 for acid leaching treatment, and dissolving out a template agent; then drying for 10h at 70 ℃ after filtering to obtain the copper-nitrogen doped hierarchical pore carbon material;
the copper-nitrogen-doped hierarchical porous carbon material obtained in the example has the copper loading of 2.46 wt.%, the nitrogen content of 5.1 wt.% and the specific surface area of 596m 2 Per g, pore volume 1.15cm 3 (wherein the pore volume ratio of the microporous structure, the mesoporous structure and the macroporous structure 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 stirring for 30min at the power of 500W and the stirring speed of 300rpm for 6h at normal temperature, centrifuging by using a centrifuge, and taking out a lower-layer 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 and dissolving 850mg of zinc nitrate hexahydrate, 50mg of manganese nitrate hexahydrate and 25mL of methanol to obtain a second mixed solution; mixing and dissolving 1g of 2-methylimidazole and 25mL of methanol to obtain a third mixed solution; dropwise adding the second mixed solution and the third mixed solution into the first mixed solution at a dropwise adding speed of 5mL/min, putting the obtained mixed solution into an oil bath pot, heating and refluxing, and carrying out a complex reaction for 12 hours at a temperature of 60 ℃; centrifuging by using a centrifuge after the reaction is finished, taking out the lower-layer precipitate, putting the precipitate into a vacuum oven at 70 ℃ for drying for 12h, taking out the precipitate, and grinding the precipitate into powder to obtain a precursor material;
placing the obtained precursor material in a tube furnace, heating to 900 ℃ at a heating rate of 10 ℃/min under the protection of 80mL/min nitrogen gas flow, and then roasting, wherein the heat preservation time is 2 h; 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 for acid leaching treatment, and dissolving out a template agent; then drying for 10h at 70 ℃ after filtering to obtain the manganese-nitrogen doped hierarchical pore carbon material;
the manganese loading amount of the manganese-nitrogen-doped hierarchical porous carbon material obtained in the embodiment is 078 wt.%, nitrogen content 10.4 wt.%, specific surface area 711m 2 Per g, pore volume 1.79cm 3 (wherein the pore volume ratio of the microporous structure, the mesoporous structure and 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, then sequentially carrying out ultrasonic treatment for 30min at the power of 500W at normal temperature and at the stirring speed of 300rpm for 6h, centrifuging by using a centrifuge, and taking out a lower-layer precipitate to obtain 622mg of a matrix material;
uniformly stirring and dispersing the obtained matrix material and 250mL of methanol to obtain a first mixed solution; mixing and dissolving 850mg of zinc nitrate hexahydrate, 50mg of ruthenium chloride and 25mL of methanol to obtain a second mixed solution; mixing and dissolving 1g of 2-methylimidazole and 25mL of methanol to obtain a third mixed solution; dropwise adding the second mixed solution and the third mixed solution into the first mixed solution at a dropwise adding speed of 5mL/min, putting the obtained mixed solution into an oil bath pot, heating and refluxing, and carrying out a complex reaction for 12 hours at a temperature of 60 ℃; centrifuging by using a centrifuge after the reaction is finished, taking out the lower-layer precipitate, putting the precipitate into a vacuum oven at 70 ℃ for drying for 12h, taking out the precipitate, and grinding the precipitate into powder to obtain a precursor material;
placing the obtained precursor material in a tube furnace, heating to 900 ℃ at a heating rate of 10 ℃/min under the protection of 80mL/min nitrogen gas flow, and then roasting, wherein the heat preservation time is 2 h; 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 for acid leaching treatment, and dissolving out a template agent; then drying for 10h at 70 ℃ after filtering to obtain the ruthenium-nitrogen doped hierarchical pore carbon material;
the ruthenium-nitrogen doped hierarchical porous carbon material obtained in the example has the loading of ruthenium of 0.64 wt.%, the nitrogen content of 6.4 wt.%, and the specific surface area of 634m 2 Per g, pore volume 1.28cm 3 (wherein the pore volume ratio of the microporous structure, the mesoporous structure and the macroporous structure 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 stirring for 30min at the power of 500W at normal temperature and at the stirring speed of 300rpm for 6h, centrifuging by using a centrifuge, and taking out a lower-layer precipitate to obtain a matrix material of 604 mg;
uniformly stirring and dispersing the obtained matrix material and 250mL of methanol to obtain a first mixed solution; mixing and dissolving 850mg of zinc nitrate hexahydrate, 50mg of silver nitrate and 25mL of methanol to obtain a second mixed solution; mixing and dissolving 1g of 2-methylimidazole and 25mL of methanol to obtain a third mixed solution; dropwise adding the second mixed solution and the third mixed solution into the first mixed solution at a dropwise adding speed of 5mL/min, putting the obtained mixed solution into an oil bath pot, heating and refluxing, and carrying out a complex reaction for 12 hours at a temperature of 60 ℃; centrifuging by using a centrifuge after the reaction is finished, taking out the lower-layer precipitate, putting the precipitate into a vacuum oven at 70 ℃ for drying for 12 hours, taking out the precipitate, and grinding the precipitate into powder to obtain a precursor material;
placing the obtained precursor material in a tube furnace, heating to 900 ℃ at a heating rate of 10 ℃/min under the protection of 80mL/min nitrogen gas flow, and then roasting, wherein the heat preservation time is 2 h; 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 for acid leaching treatment, and dissolving out a template agent; then drying the mixture for 10 hours at 70 ℃ after filtering to obtain a silver-nitrogen doped hierarchical pore carbon material;
the silver-nitrogen-doped hierarchical porous carbon material obtained in the example has the silver loading amount of 1.36 wt.%, the nitrogen content of 8.3 wt.% and the specific surface area of 664m 2 Per g, pore volume 1.52cm 3 (wherein the pore volume ratio of the microporous structure, the mesoporous structure and the macroporous structure 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 stirring for 30min at the power of 500W at normal temperature and at the stirring speed of 300rpm for 6h, centrifuging by using a centrifuge, and taking out a lower-layer precipitate to obtain 593mg of a matrix material;
uniformly stirring and dispersing the obtained precursor material and 250mL of methanol to obtain a fourth mixed solution; mixing and dissolving 5mg of silver nitrate and 25mL of methanol to obtain a fifth mixed solution; mixing and dissolving 1g of phenanthroline and 25mL of methanol to obtain a sixth mixed solution; dropwise adding the fifth mixed solution and the sixth mixed solution into the fourth mixed solution at a dropwise adding speed of 5mL/min, putting the obtained mixed solution into an oil bath pot, heating and refluxing, and carrying out a complex reaction for 12 hours at a temperature of 60 ℃; centrifuging by using a centrifuge after the reaction is finished, taking out the lower-layer precipitate, putting the precipitate into a vacuum oven at 70 ℃ for drying for 12h, taking out the precipitate, and grinding the precipitate into powder to obtain a precursor material;
placing the obtained precursor material in a tube furnace, heating to 900 ℃ at a heating rate of 10 ℃/min under the protection of 80mL/min nitrogen gas flow, and then roasting, wherein the heat preservation time is 2 h; 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 for acid leaching treatment, and dissolving out a template agent; then drying for 10 hours at 70 ℃ after filtering to obtain the silver-nitrogen doped hierarchical pore carbon material;
the silver-nitrogen-doped hierarchical porous carbon material obtained in the example has the silver loading amount of 0.88 wt.%, the nitrogen content of 6.3 wt.% and the specific surface area of 592m 2 Per g, pore volume 1.77cm 3 (wherein the pore volume ratio of the microporous structure, the mesoporous structure and the macroporous structure is 1:1: 3).
Comparative example 1
Mixing 500mg of blocky solid copper oxide, 500mg of polyvinylpyrrolidone and 100mL of methanol, sequentially carrying out ultrasonic stirring for 30min at the power of 500W and the stirring speed of 300rpm for 6h at normal temperature, centrifuging by using a centrifuge, and taking out a lower-layer precipitate to obtain 668mg of a base material;
uniformly stirring and dispersing the obtained matrix material and 250mL of methanol to obtain a first mixed solution; mixing and dissolving 850mg of zinc nitrate hexahydrate, 50mg of nickel nitrate hexahydrate and 25mL of methanol to obtain a second mixed solution; mixing and dissolving 1g of 2-methylimidazole and 25mL of methanol to obtain a third mixed solution; dropwise adding the second mixed solution and the third mixed solution into the first mixed solution at a dropwise adding speed of 5mL/min, putting the obtained mixed solution into an oil bath pot, heating and refluxing, and carrying out a complex reaction for 12 hours at a temperature of 60 ℃; centrifuging by using a centrifuge after the reaction is finished, taking out the lower-layer precipitate, putting the precipitate into a vacuum oven at 70 ℃ for drying for 12h, taking out the precipitate, and grinding the precipitate into powder to obtain a precursor material;
placing the obtained precursor material in a tube furnace, heating to 900 ℃ at a heating rate of 10 ℃/min under the protection of 80mL/min nitrogen gas flow, and then roasting, wherein the heat preservation time is 2 h; 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 for acid leaching treatment, and dissolving out a template agent; then drying for 10h at 70 ℃ after filtering to obtain a nickel-nitrogen doped blocky solid single microporous carbon material;
the loading of nickel in the nickel-nitrogen doped massive solid single microporous carbon material obtained in this example was 1.22 wt.%, the nitrogen content was 5.6 wt.%, and the specific surface area was 617m 2 Per g, pore volume 0.31cm 3 /g。
Performance testing
Test example 1
The hierarchical porous material obtained in example 1 is detected by a scanning transmission electron microscope, and the STEM detection result is shown in fig. 1, and it can be seen from fig. 1 that the hierarchical porous material obtained in this example has abundant and uniformly dispersed nickel metal unit sites.
Test example 2
Scanning electron microscope detection is carried out on the hierarchical porous material obtained in the example 1, the SEM detection result is shown in fig. 2, and it can be seen from fig. 2 that the hierarchical porous material obtained in the implementation is a micron-sized porous ball composed of countless layered nanosheets; and has rich pore channels.
Test example 3
The hierarchical porous material obtained in the embodiment 1-12 is used as a catalyst to catalyze carbon dioxide to reduce and prepare carbon monoxide, and the specific method comprises the following steps:
mixing 1.2mg of a hierarchical porous material, 564 mu L of ethanol and 36 mu L of perfluorosulfonic acid polymer solution with the mass concentration of 5% to obtain slurry;
coating the slurry on a 1 × 3cm substrate 2 On carbon paper (load amount is 0.4 mg/cm) 2 ) To obtain a catalyst electrode (I.e., the working electrode);
the catalyst electrode is used as a cathode, a 1mol/L KOH solution is used as an electrolyte, an Ag/AgCl electrode (a KCl solution of which the solvent is 3 mol/L) is used as a reference electrode, foamed 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. Under the conditions of normal temperature and normal pressure, setting the water circulation rotation speed to be 30 mL/min; CO was introduced at a rate of 20mL/min 2 Flowing for 20min to make CO 2 When the gas is saturated, performing cyclic voltammetry scanning for 30 circles, activating the catalyst and simultaneously discharging the absorbed gas; electrifying for 12min, extracting 1mL of gas for gas chromatography detection, and H 2 The Faraday efficiency and the fractional current density of the product were calculated from the measured gas content of the product, which was detected by a Thermal Conductivity Detector (TCD) in the chromatograph, CO by a hydrogen Flame Ionization Detector (FID) equipped with a nickel reformer.
Wherein FIG. 4 is a graph of the Faraday efficiency of carbon monoxide when the multi-stage porous material of example 1 is a catalyst, and FIG. 5 is a graph of the fractional current density when the multi-stage porous material of example 1 is a catalyst; from FIG. 4, it can be seen that the faradaic efficiency of Ni-N-C is greater than 90% at a wide voltage window of-0.4 to-1.3V, with a maximum value near 100% being obtained at-0.7V; as can be seen from FIG. 5, the current density of carbon monoxide exceeds 100mA cm after-0.6V -2 Reaches a maximum value of 524mA cm at-1.4V -2 ；
The test results are shown in table 1.
TABLE 1 test results of catalytic carbon dioxide reduction of the hierarchical porous materials obtained in examples 1 to 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 large faradaic efficiency of carbon monoxide at a low potential and have a large fractional current density in a reaction for preparing carbon monoxide by catalytic reduction of carbon dioxide.
Although the above embodiments have been described in detail, they are only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and all of the embodiments belong to the protection scope of the present invention.
Claims (10)
1. The preparation method of the hierarchical porous material is characterized by comprising the following steps:
mixing a template agent, a surface modifier and a polar solvent to obtain a matrix material;
growing a metal organic compound 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 porous material;
the template has a loose porous structure;
the template agent comprises one or more of metal oxide, metal salt and silicon oxide.
2. The production method according to claim 1, wherein the metal oxide comprises magnesium oxide and/or zinc oxide; the metal salt comprises basic magnesium carbonate; the oxide of silicon comprises silicon dioxide.
3. The method of claim 1, wherein the metal organic compound comprises a zeolitic imidazole framework or a metal organic complex.
4. The method of claim 3, wherein the in-situ growth comprises the following steps when the metal-organic compound is a zeolitic imidazole framework: mixing a base material, a first soluble metal salt, a second soluble metal salt, 2-methylimidazole and a polar solvent, and carrying out a 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 iron salt, soluble cobalt salt, soluble copper salt, soluble manganese salt, soluble ruthenium salt and soluble silver salt.
5. The method according to claim 3, wherein when the metal-organic compound is a metal-organic complex, the in-situ growth comprises the steps of:
mixing a base material, soluble metal salt, an organic ligand and a polar solvent, and carrying out a complex 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 matter ligand comprises one or more of phenanthroline, formamide, melamine and polyaniline.
6. The preparation method of claim 1, wherein the roasting temperature is 600-1200 ℃ and the holding time is 0.5-10 h.
7. The method according to any one of claims 1 to 6, wherein the template is replaced with polystyrene;
when the template agent is polystyrene, the preparation method of the hierarchical porous material does not comprise acid leaching treatment.
8. The hierarchical porous material prepared by the preparation method of any one of claims 1 to 7, characterized in that the hierarchical porous material is a metal-doped hierarchical porous carbon material.
9. The hierarchical pore material according to claim 8, wherein 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%.
10. Use of the hierarchical pore material of claim 8 or 9 in catalytic carbon dioxide reduction reactions.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115928107A (en) * | 2022-11-11 | 2023-04-07 | 西南科技大学 | Efficient electro-catalytic reduction of CO 2 Preparation and application of diatomic electrocatalyst for CO |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016011841A1 (en) * | 2014-07-22 | 2016-01-28 | 北京化工大学 | Unsupported catalyst and preparation method therefor and application thereof |
| CN107282081A (en) * | 2017-05-31 | 2017-10-24 | 河南师范大学 | A kind of preparation method of bulk multi-hole nitrogen-doped carbon oxygen reduction catalyst |
| US20190067706A1 (en) * | 2017-08-29 | 2019-02-28 | Uchicago Argonne, Llc | Carbon dioxide reduction electro catalysts prepared for metal organic frameworks |
| CN110813359A (en) * | 2019-11-22 | 2020-02-21 | 福州大学 | Ruthenium-based ammonia synthesis catalyst with nitrogen-doped porous carbon material as carrier and preparation method thereof |
| CN110918112A (en) * | 2018-09-19 | 2020-03-27 | 国家纳米科学中心 | Carbon dioxide electrochemical reduction catalyst and preparation method and application thereof |
| CN111871406A (en) * | 2020-08-07 | 2020-11-03 | 湖南大学 | Catalyst for preparing synthesis gas by electrochemical reduction of carbon dioxide and preparation method thereof |
| CN112663086A (en) * | 2021-01-04 | 2021-04-16 | 中科院过程工程研究所南京绿色制造产业创新研究院 | Ni-N-C monatomic catalyst and preparation method and application thereof |
| CN112786906A (en) * | 2021-01-28 | 2021-05-11 | 安徽理工大学 | Porous Fe-Co-N doped porous carbon catalyst and preparation method and application thereof |
| CN113262824A (en) * | 2021-04-27 | 2021-08-17 | 广州紫科环保科技股份有限公司 | Preparation of composite photocatalyst and application of composite photocatalyst in VOCs purification |
| CN113979425A (en) * | 2021-10-21 | 2022-01-28 | 河北中煤旭阳能源有限公司 | Co/N double-doped carbon nanoribbon and Li-SeS2Battery positive electrode material, preparation method thereof and secondary battery |
-
2022
- 2022-06-14 CN CN202210668347.8A patent/CN114892196B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016011841A1 (en) * | 2014-07-22 | 2016-01-28 | 北京化工大学 | Unsupported catalyst and preparation method therefor and application thereof |
| CN107282081A (en) * | 2017-05-31 | 2017-10-24 | 河南师范大学 | A kind of preparation method of bulk multi-hole nitrogen-doped carbon oxygen reduction catalyst |
| US20190067706A1 (en) * | 2017-08-29 | 2019-02-28 | Uchicago Argonne, Llc | Carbon dioxide reduction electro catalysts prepared for metal organic frameworks |
| CN110918112A (en) * | 2018-09-19 | 2020-03-27 | 国家纳米科学中心 | Carbon dioxide electrochemical reduction catalyst and preparation method and application thereof |
| CN110813359A (en) * | 2019-11-22 | 2020-02-21 | 福州大学 | Ruthenium-based ammonia synthesis catalyst with nitrogen-doped porous carbon material as carrier and preparation method thereof |
| CN111871406A (en) * | 2020-08-07 | 2020-11-03 | 湖南大学 | Catalyst for preparing synthesis gas by electrochemical reduction of carbon dioxide and preparation method thereof |
| CN112663086A (en) * | 2021-01-04 | 2021-04-16 | 中科院过程工程研究所南京绿色制造产业创新研究院 | Ni-N-C monatomic catalyst and preparation method and application thereof |
| CN112786906A (en) * | 2021-01-28 | 2021-05-11 | 安徽理工大学 | Porous Fe-Co-N doped porous carbon catalyst and preparation method and application thereof |
| CN113262824A (en) * | 2021-04-27 | 2021-08-17 | 广州紫科环保科技股份有限公司 | Preparation of composite photocatalyst and application of composite photocatalyst in VOCs purification |
| CN113979425A (en) * | 2021-10-21 | 2022-01-28 | 河北中煤旭阳能源有限公司 | Co/N double-doped carbon nanoribbon and Li-SeS2Battery positive electrode material, preparation method thereof and secondary battery |
Non-Patent Citations (3)
| Title |
|---|
| CHEN, YIQUN等: ""Hierarchical Ni/N/C Single-Site Catalyst Achieving Industrial-Level Current Density and Ultra-Wide Potential Plateau of High CO Faradic Efficiency for CO2 Electroreduction"", 《ADVANCED FUNCTIONAL MATERIALS》, pages 2214658 * |
| HU, XIN-MING等: ""Selective CO2 Reduction to CO in Water using Earth-Abundant Metal and Nitrogen-Doped Carbon Electrocatalysts"", 《ACS CATALYSIS》, vol. 8, pages 6261 * |
| 郭治良: ""基于金属有机框架ZIFs衍生材料的制备及其电催化还原CO2性能研究"", 《中国优秀硕士学位论文全文数据库 工程科技I辑》, pages 016 - 638 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115928107A (en) * | 2022-11-11 | 2023-04-07 | 西南科技大学 | Efficient electro-catalytic reduction of CO 2 Preparation and application of diatomic electrocatalyst for CO |
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