CN114632533B - Sub-nanometer metal catalyst and preparation method and application method thereof - Google Patents
Sub-nanometer metal catalyst and preparation method and application method thereof Download PDFInfo
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- CN114632533B CN114632533B CN202210225830.9A CN202210225830A CN114632533B CN 114632533 B CN114632533 B CN 114632533B CN 202210225830 A CN202210225830 A CN 202210225830A CN 114632533 B CN114632533 B CN 114632533B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 230
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 182
- 239000002184 metal Substances 0.000 title claims abstract description 182
- 238000000034 method Methods 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- -1 phenolic acid compound Chemical class 0.000 claims abstract description 81
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 71
- 239000002904 solvent Substances 0.000 claims abstract description 45
- 238000001354 calcination Methods 0.000 claims abstract description 44
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims abstract description 42
- 239000002243 precursor Substances 0.000 claims abstract description 35
- 238000003756 stirring Methods 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 32
- 238000001035 drying Methods 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 18
- 239000011593 sulfur Substances 0.000 claims abstract description 18
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 230000001681 protective effect Effects 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 80
- 239000010941 cobalt Substances 0.000 claims description 80
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 80
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 229910052799 carbon Inorganic materials 0.000 claims description 24
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 22
- 238000000227 grinding Methods 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 15
- 239000000725 suspension Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 229940074391 gallic acid Drugs 0.000 claims description 12
- 235000004515 gallic acid Nutrition 0.000 claims description 12
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 239000002351 wastewater Substances 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 10
- 230000000536 complexating effect Effects 0.000 claims description 10
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 10
- 239000011943 nanocatalyst Substances 0.000 claims description 9
- 239000003344 environmental pollutant Substances 0.000 claims description 8
- 231100000719 pollutant Toxicity 0.000 claims description 8
- 229910052723 transition metal Inorganic materials 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 238000002336 sorption--desorption measurement Methods 0.000 claims description 7
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical compound SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002778 food additive Substances 0.000 claims description 4
- 235000013373 food additive Nutrition 0.000 claims description 4
- 239000000575 pesticide Substances 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- KSEBMYQBYZTDHS-HWKANZROSA-M (E)-Ferulic acid Natural products COC1=CC(\C=C\C([O-])=O)=CC=C1O KSEBMYQBYZTDHS-HWKANZROSA-M 0.000 claims description 3
- CWVRJTMFETXNAD-FWCWNIRPSA-N 3-O-Caffeoylquinic acid Natural products O[C@H]1[C@@H](O)C[C@@](O)(C(O)=O)C[C@H]1OC(=O)\C=C\C1=CC=C(O)C(O)=C1 CWVRJTMFETXNAD-FWCWNIRPSA-N 0.000 claims description 3
- PZIRUHCJZBGLDY-UHFFFAOYSA-N Caffeoylquinic acid Natural products CC(CCC(=O)C(C)C1C(=O)CC2C3CC(O)C4CC(O)CCC4(C)C3CCC12C)C(=O)O PZIRUHCJZBGLDY-UHFFFAOYSA-N 0.000 claims description 3
- CWVRJTMFETXNAD-KLZCAUPSSA-N Neochlorogenin-saeure Natural products O[C@H]1C[C@@](O)(C[C@@H](OC(=O)C=Cc2ccc(O)c(O)c2)[C@@H]1O)C(=O)O CWVRJTMFETXNAD-KLZCAUPSSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 230000003115 biocidal effect Effects 0.000 claims description 3
- 235000001368 chlorogenic acid Nutrition 0.000 claims description 3
- CWVRJTMFETXNAD-JUHZACGLSA-N chlorogenic acid Chemical compound O[C@@H]1[C@H](O)C[C@@](O)(C(O)=O)C[C@H]1OC(=O)\C=C\C1=CC=C(O)C(O)=C1 CWVRJTMFETXNAD-JUHZACGLSA-N 0.000 claims description 3
- 229940074393 chlorogenic acid Drugs 0.000 claims description 3
- FFQSDFBBSXGVKF-KHSQJDLVSA-N chlorogenic acid Natural products O[C@@H]1C[C@](O)(C[C@@H](CC(=O)C=Cc2ccc(O)c(O)c2)[C@@H]1O)C(=O)O FFQSDFBBSXGVKF-KHSQJDLVSA-N 0.000 claims description 3
- BMRSEYFENKXDIS-KLZCAUPSSA-N cis-3-O-p-coumaroylquinic acid Natural products O[C@H]1C[C@@](O)(C[C@@H](OC(=O)C=Cc2ccc(O)cc2)[C@@H]1O)C(=O)O BMRSEYFENKXDIS-KLZCAUPSSA-N 0.000 claims description 3
- 235000001785 ferulic acid Nutrition 0.000 claims description 3
- KSEBMYQBYZTDHS-HWKANZROSA-N ferulic acid Chemical compound COC1=CC(\C=C\C(O)=O)=CC=C1O KSEBMYQBYZTDHS-HWKANZROSA-N 0.000 claims description 3
- 229940114124 ferulic acid Drugs 0.000 claims description 3
- KSEBMYQBYZTDHS-UHFFFAOYSA-N ferulic acid Natural products COC1=CC(C=CC(O)=O)=CC=C1O KSEBMYQBYZTDHS-UHFFFAOYSA-N 0.000 claims description 3
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 3
- QURCVMIEKCOAJU-UHFFFAOYSA-N trans-isoferulic acid Natural products COC1=CC=C(C=CC(O)=O)C=C1O QURCVMIEKCOAJU-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 abstract description 11
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- 238000006731 degradation reaction Methods 0.000 abstract description 10
- 239000000243 solution Substances 0.000 description 46
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 229940090668 parachlorophenol Drugs 0.000 description 20
- 230000003197 catalytic effect Effects 0.000 description 17
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- 229910052742 iron Inorganic materials 0.000 description 9
- 239000011572 manganese Substances 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
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- 239000010453 quartz Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000002019 doping agent Substances 0.000 description 4
- 230000000670 limiting effect Effects 0.000 description 4
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- 238000010525 oxidative degradation reaction Methods 0.000 description 4
- 208000012868 Overgrowth Diseases 0.000 description 3
- 230000004075 alteration Effects 0.000 description 3
- 229910001429 cobalt ion Inorganic materials 0.000 description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
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- 239000004570 mortar (masonry) Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000003642 reactive oxygen metabolite Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- LINPIYWFGCPVIE-UHFFFAOYSA-N 2,4,6-trichlorophenol Chemical compound OC1=C(Cl)C=C(Cl)C=C1Cl LINPIYWFGCPVIE-UHFFFAOYSA-N 0.000 description 1
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- MPVDXIMFBOLMNW-ISLYRVAYSA-N 7-hydroxy-8-[(E)-phenyldiazenyl]naphthalene-1,3-disulfonic acid Chemical compound OC1=CC=C2C=C(S(O)(=O)=O)C=C(S(O)(=O)=O)C2=C1\N=N\C1=CC=CC=C1 MPVDXIMFBOLMNW-ISLYRVAYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004100 Oxytetracycline Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000004098 Tetracycline Substances 0.000 description 1
- 238000000779 annular dark-field scanning transmission electron microscopy Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- FFGPTBGBLSHEPO-UHFFFAOYSA-N carbamazepine Chemical compound C1=CC2=CC=CC=C2N(C(=O)N)C2=CC=CC=C21 FFGPTBGBLSHEPO-UHFFFAOYSA-N 0.000 description 1
- 229960000623 carbamazepine Drugs 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
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- 238000005087 graphitization Methods 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 1
- 229940107698 malachite green Drugs 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 229960000625 oxytetracycline Drugs 0.000 description 1
- IWVCMVBTMGNXQD-PXOLEDIWSA-N oxytetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3[C@H](O)[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-PXOLEDIWSA-N 0.000 description 1
- 235000019366 oxytetracycline Nutrition 0.000 description 1
- 229960003742 phenol Drugs 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 241000894007 species Species 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- IWVCMVBTMGNXQD-UHFFFAOYSA-N terramycin dehydrate Natural products C1=CC=C2C(O)(C)C3C(O)C4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-UHFFFAOYSA-N 0.000 description 1
- 229960002180 tetracycline Drugs 0.000 description 1
- 235000019364 tetracycline Nutrition 0.000 description 1
- 229930101283 tetracycline Natural products 0.000 description 1
- 150000003522 tetracyclines Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a sub-nanometer metal catalyst and a preparation method and an application method thereof, wherein the preparation method comprises the following steps: dispersing: dispersing a phenolic acid compound and a transition metal compound in a first solvent to form a metal-phenolic acid complex solution; doping: adding a nitrogen-containing sulfur source into the metal-phenolic acid complex solution, heating to a preset temperature, stirring until the first solvent volatilizes, and drying to obtain a metal precursor mixture; calcining: calcining the metal precursor mixture in a protective gas atmosphere, and cooling to room temperature to obtain the sub-nano metal catalyst. The preparation method can improve the uniformity of the particles of the sub-nano metal catalyst, and the sub-nano metal catalyst has high efficiency and good stability in catalyzing the degradation of organic pollutants by the peroxymonosulfate.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a sub-nanometer metal catalyst and a preparation method and an application method thereof.
Background
Peroxymonosulfate (PMS) is capable of being activated under the catalytic action of a catalyst at near-ambient temperature and pressure to produce reactive oxygen species (e.g., hydroxyl radicals and sulfate radicals) with strong oxidizing properties, and is often used to decompose organic contaminants in sewage.
However, the catalysts of the related art have problems of low stability and low catalytic performance, resulting in low efficiency in catalyzing the decomposition of organic pollutants by peroxymonosulfate.
Disclosure of Invention
The embodiment of the invention discloses a sub-nanometer metal catalyst, a preparation method and an application method thereof, wherein the catalyst prepared by the preparation method has high stability, good catalytic performance and high efficiency of catalyzing organic pollutants by peroxymonosulfate.
To achieve the above object, in a first aspect, an embodiment of the present invention discloses a method for preparing a sub-nano metal catalyst, the method comprising the steps of:
complexing: dispersing phenolic acid compounds and transition metal compounds in a first solvent to form a metal-phenolic acid complex solution;
doping: adding a nitrogen-containing sulfur source into the metal-phenolic acid complex solution, stirring at 50-100 ℃ until the first solvent volatilizes, and drying to obtain a metal precursor mixture;
calcining: calcining the metal precursor mixture in a protective gas atmosphere, and cooling to room temperature to obtain the sub-nano metal catalyst.
As an alternative embodiment, in the example of the first aspect of the invention, the complexing step is:
Phenolic acid compound dispersion: dispersing the phenolic acid compound in a second solvent to form a phenolic acid compound suspension;
dispersing a transition metal compound: dispersing the transition metal compound in a third solvent to form a transition metal compound solution;
mixing: the transition metal compound solution and the transition metal compound solution are uniformly mixed to form the metal-phenolic acid complex solution.
As an alternative embodiment, in the example of the first aspect of the present invention, before the calcining step, the preparation method further includes:
grinding: the metal precursor mixture is ground to a powder.
As an alternative embodiment, in the example of the first aspect of the present invention, the step of calcining is:
and heating the metal precursor mixture to 650-1050 ℃ at a heating rate of 1-15 ℃/min under the protective gas atmosphere, calcining, and cooling to room temperature to obtain the sub-nano metal catalyst.
As an alternative embodiment, in the example of the first aspect of the present invention, after the step of calcining, the preparation method further includes:
Washing: washing the sub-nano metal catalyst with a fourth solvent to remove impurities of the sub-nano metal catalyst, and drying and grinding to form the powdery sub-nano metal catalyst.
As an alternative embodiment, in the example of the first aspect of the present invention, the phenolic acid compound includes one or more of gallic acid, chlorogenic acid, gallic acid, ferulic acid, and mesonic acid;
the transition metal element in the transition metal compound comprises one or more of iron element, cobalt element, nickel element, copper element and manganese element;
the nitrogen-sulfur-containing source comprises one or more of cyanuric acid, thiocyanic acid, thiourea and thioacetamide.
As an alternative embodiment, in the example of the first aspect of the present invention, the mass ratio of the transition metal compound to the phenolic acid compound is 1:1 to 1:10; and/or the number of the groups of groups,
the mass ratio of the nitrogen-containing sulfur source to the phenolic acid compound is 1:10-1:30.
In a first aspect, an embodiment of the invention discloses a sub-nano metal catalyst, which is prepared by adopting the preparation method of the sub-nano metal catalyst in the first aspect, wherein the sub-nano metal catalyst is a transition metal-loaded sulfur-nitrogen co-doped carbon-based sub-nano catalyst.
In a third aspect, an embodiment of the present invention discloses an application method of the sub-nano metal catalyst according to the second aspect, where the application method includes:
dispersing the sub-nano metal catalyst in wastewater containing organic pollutants, stirring until the sub-nano metal catalyst and the organic pollutants reach an adsorption-desorption equilibrium state, and adding peroxymonosulfate to decompose the organic pollutants.
In an alternative embodiment, in an example of the third aspect of the invention, the pH of the wastewater is between 2 and 14, and/or,
the organic pollutants comprise one or more of organic dye pollutants, antibiotic pollutants, organic pesticide pollutants and food additive pollutants.
As an alternative embodiment, in the example of the third aspect of the present invention, the mass ratio of the sub-nano metal catalyst to the peroxymonosulfate is 200:317 to 20:317; and/or the number of the groups of groups,
the molar ratio of the organic pollutant to the peroxymonosulfate is 1:1-20:1.
Compared with the prior art, the embodiment of the invention has the beneficial effects that:
according to the preparation method of the sub-nano metal catalyst, the phenolic acid compound is used as a carbon source, and the in-situ growth of small metal particles on the phenolic acid compound-derived carbon carrier can be realized by utilizing the strong complexing capacity of the phenolic acid compound to transition metal ions and the limited domain effect in the carbonization process. The adopted nitrogen-containing sulfur source can modify the carbon carrier through sulfur doping, further limit aggregation of metal on the surface of the carbon carrier, and improve the uniformity of particles of the sub-nano metal catalyst. In addition, the preparation method utilizes the strong complexing action of phenolic acid compounds on metal ions and the strong binding capacity of sulfur dopants on metal atoms to limit the overgrowth of metal particles on a carbon carrier. The research shows that the simultaneous use of phenolic acid compounds and sulfur dopants is very important, and is an important condition for ensuring the formation of the carbon-supported sub-nano metal catalyst. The sub-nano metal catalyst is used for degrading and removing organic pollutants by activating the peroxymonosulfate, has the advantages of mild reaction conditions (room temperature), high organic pollutant removing efficiency, good nano metal catalyst stability and less heavy metal ion dissolution, and is superior to the traditional nano metal catalyst and metal oxide catalyst in terms of degradation efficiency and metal ion dissolution.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a representation of a sub-nano cobalt catalyst in the first example;
FIG. 2 is an X-ray diffraction pattern, an X-ray photoelectron spectrum, a nitrogen adsorption-desorption isotherm map and a pore diameter distribution map of a sub-nano cobalt catalyst in the first embodiment;
FIG. 3 is a graph showing the dissolution of cobalt ions when the sub-nanometer cobalt catalyst in the first example catalyzes the degradation of p-chlorophenol by peroxymonosulfate;
FIG. 4 is a graph showing the catalytic recycling performance of the sub-nanometer cobalt catalyst in the first embodiment;
FIG. 5 is an X-ray diffraction pattern of four sub-nano metal catalysts in the second to fourth embodiments;
FIG. 6 is a HAADF-STEM diagram of spherical aberration correction of four sub-nano metal catalysts in second through fourth embodiments;
FIG. 7 is a graph showing the effectiveness of the four sub-nano metal catalysts of the second to fourth embodiments in catalyzing the degradation of p-chlorophenol by peroxymonosulfate;
FIG. 8 is a transmission electron microscope image of a sub-nano metal catalyst in comparative example one;
FIG. 9 is a graph showing the efficacy of parachlorophenol degradation in examples one, two and three;
fig. 10 is a graph of performance versus performance of the sub-nano cobalt catalyst in example one versus the cobalt nano catalyst in comparative example four.
Detailed Description
In the present invention, the terms "upper", "lower", "left", "right", "front", "rear", "top", "bottom", "inner", "outer", "middle", "vertical", "horizontal", "lateral", "longitudinal" and the like indicate an azimuth or a positional relationship based on that shown in the drawings. These terms are only used to better describe the present invention and its embodiments and are not intended to limit the scope of the indicated devices, elements or components to the particular orientations or to configure and operate in the particular orientations.
Also, some of the terms described above may be used to indicate other meanings in addition to orientation or positional relationships, for example, the term "upper" may also be used to indicate some sort of attachment or connection in some cases. The specific meaning of these terms in the present invention will be understood by those of ordinary skill in the art according to the specific circumstances.
Furthermore, the terms "mounted," "configured," "provided," "connected," and "connected" are to be construed broadly. For example, it may be a fixed connection, a removable connection, or a unitary construction; may be a mechanical connection, or an electrical connection; may be directly connected, or indirectly connected through intervening media, or may be in internal communication between two devices, elements, or components. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
Furthermore, the terms "first," "second," and the like, are used primarily to distinguish between different devices, elements, or components (the particular species and configurations may be the same or different), and are not used to indicate or imply the relative importance and number of devices, elements, or components indicated. Unless otherwise indicated, the meaning of "a plurality" is two or more.
With the continuous development of industrialization and urban production, the water environment is discharged with various complex organic pollutants, such as organic dyes used in manufacturing industry, antibiotics used in medical industry, organic pesticides used in agriculture, food additives used in food processing, and the like, which are difficult to biodegrade and pose serious threat to ecological balance. Therefore, the treatment of sewage is an important issue at present.
Peroxymonosulfate (PMS), when activated, is capable of generating reactive oxygen species (e.g., hydroxyl radicals and sulfate radicals) with strong oxidizing properties at near-ambient temperatures and pressures, and is thus used in wastewater remediation to decompose organic contaminants in wastewater.
In the related art, nano metal catalysts or metal oxide catalysts are often used to catalyze the peroxymonosulfate, so that the peroxymonosulfate can decompose organic pollutants in sewage at near-ambient temperature and pressure. However, the nano metal catalyst or the metal oxide catalyst still has the problems of difficult control of particle size and distribution, low metal loading, serious metal ion dissolution and the like, and has the problems of low catalytic efficiency and very low organic pollutant decomposition efficiency when the nano metal catalyst or the metal oxide catalyst is applied to decomposing organic pollutants in sewage.
Based on the above, the application provides a sub-nanometer metal catalyst, a preparation method and an application method thereof, so as to solve the problems.
The application discloses a preparation method of a sub-nanometer metal catalyst, which comprises the following steps:
complexing: dispersing phenolic acid compounds and transition metal compounds in a first solvent to form a metal-phenolic acid complex solution;
Doping: adding a nitrogen-containing sulfur source into the metal-phenolic acid complex solution, stirring at 50-100 ℃ until the first solvent volatilizes, and drying to obtain a metal precursor mixture;
calcining: calcining the metal precursor mixture in a protective gas atmosphere, and cooling to room temperature to obtain the sub-nano metal catalyst.
According to the preparation method of the sub-nanometer metal catalyst, phenolic acid compounds are used as carbon sources, and the in-situ growth of small metal particles on phenolic acid compound-derived carbon carriers can be realized by utilizing the strong complexing capacity of the phenolic acid compounds on transition metal ions and the limiting effect in the carbonization process. The adopted nitrogen-containing sulfur source can modify the carbon carrier through sulfur doping, further limit aggregation of metal on the surface of the carbon carrier, and improve the uniformity of particles of the sub-nano metal catalyst.
In addition, the preparation method utilizes the strong complexing action of phenolic acid compounds on metal ions and the strong binding capacity of sulfur dopants on metal atoms to limit the overgrowth of metal particles on a carbon carrier. The research shows that the simultaneous use of phenolic acid compounds and sulfur dopants is very important, and is an important condition for ensuring the formation of the carbon-supported sub-nano metal catalyst.
The sub-nano metal catalyst is used for degrading and removing organic pollutants by activating the peroxymonosulfate, has the advantages of mild reaction conditions (room temperature), high organic pollutant removing efficiency, good nano metal catalyst stability and less heavy metal ion dissolution, and is superior to the traditional nano metal catalyst and metal oxide catalyst in terms of degradation efficiency and metal ion dissolution.
It will be appreciated that the phenolic acid compound is dispersed in the solvent at a slower rate and the transition metal compound is dispersed in the solvent at a faster rate, and therefore, in order to improve the uniformity of mixing of the phenolic acid compound and the transition metal compound in the metal-phenolic acid complex solution, in some embodiments, the steps of complexing are:
phenolic acid compound dispersion: dispersing phenolic acid compounds in a second solvent to form a phenolic acid compound suspension;
dispersing a transition metal compound: dispersing a transition metal compound in a third solvent to form a transition metal compound solution;
mixing: the transition metal compound solution and the transition metal compound solution are uniformly mixed to form a metal-phenolic acid complex solution.
The phenolic acid compound is dispersed in the second solvent to form phenolic acid compound suspension, the transition metal compound is dispersed in the third solvent to form transition metal compound solution, and then the phenolic acid compound suspension and the transition metal compound solution are uniformly mixed, so that the dispersion time of the phenolic acid compound and the dispersion time of the transition metal compound can be controlled respectively to ensure that the phenolic acid compound and the transition metal compound can be uniformly dispersed in the metal-phenolic acid complex solution.
Specifically, the steps of complexation are:
phenolic acid compound dispersion: adding phenolic acid compounds into a second solvent, performing ultrasonic dispersion, and stirring at the temperature of 70-100 ℃ and the rotating speed of 300-700 rpm to obtain phenolic acid compound suspension;
dispersing a transition metal compound: adding a transition metal compound into a third solvent, performing ultrasonic dispersion, and stirring at a rotation speed of 300-700 rpm at room temperature to obtain a transition metal compound solution;
mixing: mixing the phenolic acid compound suspension and the transition metal compound solution, performing ultrasonic dispersion, and stirring at the rotation speed of 300-700 rpm at room temperature until the phenolic acid compound suspension and the transition metal compound solution are uniformly mixed to obtain the metal-phenolic acid complex solution.
Optionally, in the step of dispersing the phenolic acid compound, the following specific parameters are included:
the phenolic acid compound can be one or more of gallic acid, chlorogenic acid, gallic acid, ferulic acid and mesonic acid, and the proper phenolic acid compound can be adopted to ensure the synthesized sub-nano metal catalyst with better catalytic effect.
The mass ratio of the phenolic acid compound to the second solvent is 50:1 to 300:1, and exemplary mass ratios of the phenolic acid compound to the second solvent are 50:1, 100:1, 200:1, 300:1, and the like. The mass ratio of the phenolic acid compound to the second solvent is set so as to ensure that the phenolic acid compound can be uniformly dispersed in the second solvent.
The second solvent can be used to disperse the phenolic acid compound, and the second solvent and the third solvent can include one or more of ethanol, deionized water, methanol, or acetone, for example.
The ultrasonic dispersion time may be 1min to 10min, and for example, the ultrasonic dispersion time is 1min, 3min, 5min, 8min, 10min, etc., so as to promote the phenolic acid compound to be sufficiently dispersed in the second solvent.
The dispersion temperature in the step of dispersing the phenolic acid compound may include any point value within the temperature range, such as 70 ℃, 80 ℃, 90 ℃, 100 ℃, etc., to increase the rate at which the phenolic acid compound is sufficiently dispersed in the second solvent. The stirring speed of 300rpm to 700rpm may include any value within the range of speeds, such as 300rpm, 500rpm, 700rpm, etc., to facilitate adequate dispersion of the phenolic acid compound in the second solvent.
The stirring time may be 10min to 60min, and exemplary stirring time is 10min, 20min, 40min, 60min, etc.
Optionally, in the step of dispersing the transition metal compound, the following specific parameters are included:
the transition metal element in the transition metal compound includes one or more of iron element, cobalt element, nickel element, copper element, manganese element, and illustratively, the transition metal compound contains Fe (NO 3 ) 3 ·9H 2 O、Co(NO 3 ) 2 ·6H 2 O、Ni(NO 3 ) 2 ·6H 2 O、Cu(NO 3 ) 2 ·3H 2 O and Mn (NO) 3 ) 2 ·4H 2 One or more of O. By adopting a suitable transition metal compound, a sub-nano metal catalyst with better catalytic effect can be ensured.
The third solvent may be the same as or different from the second solvent, and may be used to disperse the phenolic acid compound, and may include one or more of ethanol, deionized water, methanol, or acetone, for example.
In order to improve the dissolution sufficiency of the transition metal, the mass ratio of the transition metal compound to the third solvent may be 1:50 to 1:200, and illustratively, the mass ratio of the transition metal compound to the third solvent is 1:50, 1:100, 1:150, 1:200, or the like.
Further, the mass ratio of the transition metal compound to the phenolic acid compound may be 1:1 to 1:10, and illustratively, the mass ratio of the transition metal compound to the phenolic acid compound is 1:1, 1:4, 1:8, 1:10, etc. By limiting the mass ratio of the transition metal compound and the phenolic acid compound, the reaction can be made to sufficiently occur after the transition metal compound and the phenolic acid compound are mixed.
The time of ultrasonic dispersion may be 1 to 5 minutes, and illustratively, the time of ultrasonic dispersion is 1, 3, 5, etc., to promote sufficient dispersion of the transition metal compound in the third solvent.
The stirring speed of 300rpm to 700rpm includes any value within the range of the rotational speed, for example, 300rpm, 500rpm, 700rpm, etc., to promote the adequate dispersion of the transition metal compound in the third solvent. The stirring time may be 1min to 10min, and exemplary stirring time is 1min, 5min, 8min, 10min, etc.
Optionally, in the step of mixing, the following specific parameters are included:
the ultrasonic dispersion time is 1min to 3min, and the ultrasonic dispersion time is 1min, 2min, 3min and the like, for example, so as to promote the phenolic acid compound and the transition metal compound to be fully and uniformly mixed.
The stirring speed may be 300rpm to 700rpm including any value within the range of speeds, such as 300rpm, 500rpm, 700rpm, etc., to promote thorough mixing of the phenolic acid compound and the transition metal compound. The stirring time may be 10min to 60min, and exemplary stirring time is 10min, 20min, 40min, 60min, etc.
The phenolic acid compound dispersing step and the transition metal compound dispersing step are not sequential, and the phenolic acid compound dispersing step and the transition metal compound dispersing step may be performed first, or the transition metal compound dispersing step may be performed first, and the phenolic acid compound dispersing step may be performed first, or the phenolic acid compound dispersing step may be performed simultaneously with the transition metal compound dispersing step.
In the doping step, the nitrogen-sulfur-containing source includes one or more of cyanuric acid, thiocyanic acid, thiourea and thioacetamide. By adopting a proper nitrogen-containing sulfur source, the sulfur-nitrogen co-doped sub-nano metal catalyst can be obtained after doping and calcining, the sulfur-nitrogen co-doped sub-nano metal catalyst has good stability and better particle uniformity, and when the sub-nano metal catalyst is used for decomposing organic pollutants in sewage, heavy metal ions are less dissolved out and the catalytic effect is good.
Alternatively, the mass ratio of the nitrogen-containing sulfur source to the phenolic acid compound is 1:10 to 1:30, and illustratively, the mass ratio of the nitrogen-containing sulfur source to the phenolic acid compound is 1:1, 1:10, 1:20, 1:30, etc.
In the doping step, the temperature at the time of stirring is 50 to 100℃including any point value within the temperature range, for example, 50℃70℃90℃100℃and the like.
Optionally, in the doping step, drying may be performed after the first solvent is completely volatilized. The temperature of the drying may be 50 to 90 ℃, and illustratively, the temperature of the drying is 50 ℃, 70 ℃, 90 ℃, etc. The drying time may be 6 to 24 hours, and illustratively, the drying time is 6, 8, 10, 15, 20, 24 hours, etc. Specifically, the calcining step is as follows:
And (3) placing the metal precursor mixture in a quartz boat, covering a cover, placing the quartz boat in a tube furnace, heating to 650-1050 ℃ at a heating rate of 1-15 ℃ per minute under a protective atmosphere, calcining, and naturally cooling to room temperature to obtain the sub-nano metal catalyst.
Optionally, in the calcining step, the following specific parameters are included:
the protective gas atmosphere may be one or more of nitrogen, argon or helium.
The heating rate may be any point value within a range of 1 deg.C/min to 15 deg.C/min, for example, the heating rate is 1 deg.C/min, 5 deg.C/min, 10 deg.C/min, 15 deg.C/min, etc. The heating rate is limited to be 1-15 ℃ per minute, so that phenolic acid compounds can be more completely graphitized, the specific surface area of the prepared sub-nano metal catalyst can be increased, and the catalytic effect can be improved.
The calcination temperature may be any value within 650 to 1050 ℃, and illustratively, the calcination temperature is 650 ℃, 700 ℃, 900 ℃, 1000 ℃, 1050 ℃, or the like. The calcination time may be 0.5 to 3 hours, and illustratively, the calcination time is 0.5 hours, 1 hour, 2 hours, 3 hours, etc. By setting the calcining temperature and the calcining time, the phenolic acid compound is ensured to be fully carbonized to form a carbon carrier with high conductivity and large surface area so as to load more catalytic metal atoms, and meanwhile, the sub-nano metal catalyst with better particle uniformity and better catalytic performance can be formed. If the calcination temperature is lower than 650 ℃ or the calcination time is less than 0.5h, phenolic hydroxyl groups of phenolic acid compounds cannot be fully decomposed, the graphitization degree is not high enough, the conductivity of the formed carbon carrier is not high enough, the surface area is not large enough, and the supported catalytic metal atoms are fewer, so that the conductivity of the sub-nano metal catalyst is affected. If the calcination temperature is higher than 1050 ℃ or the calcination time is longer than 3 hours, the catalytic metal atoms are aggregated into larger particles, and the sub-nano metal catalyst cannot be formed.
It will be appreciated that when the amount of sub-nanometer produced is relatively large, the amount of metal precursor mixture required is also relatively large, often requiring multiple calcination steps, in order to improve the uniformity and homogeneity of the phenolic acid compound, transition metal compound, nitrogen-containing sulfur source, and reaction product components thereof in each calcined metal precursor mixture, in some embodiments, the production process further comprises, prior to the calcination step:
grinding: the metal precursor mixture is ground to a powder.
By grinding the metal precursor mixture, on one hand, uniformity and consistency of each component in the metal precursor mixture in the calcination process can be improved, so that the sub-nano metal catalyst which can fully react and be prepared for many times in the calcination process has better consistency, and on the other hand, by grinding the metal precursor mixture, particles of the metal precursor mixture are finer, and uniformity and sufficiency of reaction in the calcination process can be promoted.
Specifically, the metal precursor mixture is ground for 10 min-30 min by a planetary ball mill at a rotation speed of 100 rpm-600 rpm, so as to ensure that the metal precursor mixture is sufficiently ground.
In some embodiments, after the step of calcining, the method of making further comprises:
washing: washing the sub-nano metal catalyst with a fourth solvent to remove impurities of the sub-nano metal catalyst, and drying and grinding to form the powdery sub-nano metal catalyst.
On the one hand, impurities after reaction in the sub-nano metal catalyst can be removed through the fourth solvent washing, and on the other hand, the pH value of the surface of the sub-nano metal catalyst can be adjusted, so that the influence on the pH value of the sewage is avoided when the sub-nano catalyst is used for decomposing organic pollutants in the sewage.
Specifically, in the washing step, the fourth solvent may include one or more of methanol, ethanol, and deionized water, and the drying temperature may be 40 to 90 ℃ and the drying time may be 6 to 24 hours.
The application also provides a sub-nano metal catalyst, which is prepared by adopting the preparation method of the nano metal catalyst, and the sub-nano metal catalyst is a sulfur-nitrogen co-doped carbon-based sub-nano catalyst loaded with transition metal.
The application also provides an application method of the sub-nanometer metal catalyst, which comprises the following steps:
Dispersing the sub-nanometer metal catalyst in the wastewater containing the organic pollutants, stirring until the sub-nanometer metal catalyst and the organic pollutants reach an adsorption-desorption equilibrium state, and adding the peroxymonosulfate to decompose the organic pollutants.
Alternatively, the pH of the wastewater is 2 to 14, and illustratively, the pH of the wastewater is 2, 6, 10, 14, etc. The pH of the wastewater is controlled to ensure that the sub-nano metal catalyst has better activity under the pH of the wastewater, so that the peroxymonosulfate is effectively catalyzed to fully decompose organic pollutants.
Optionally, the mass ratio of the sub-nano metal catalyst to the peroxymonosulfate is 200:317-20:317; and/or the molar ratio of the organic pollutant to the peroxymonosulfate is 1:1-20:1. Illustratively, the mass ratio of the sub-nano metal catalyst to the peroxymonosulfate is 200:317, 100:317, 50:317, 20:317, etc., and the molar ratio of the organic contaminant to the peroxymonosulfate is 1:1, 5:1, 10:15, 15:1, 20:1, etc. By setting the mass ratio of the sub-nanometer metal catalyst to the peroxymonosulfate and the mole ratio of the organic pollutant to the peroxymonosulfate, the sub-nanometer catalyst can be ensured to fully catalyze the peroxymonosulfate and the peroxymonosulfate to fully decompose the organic pollutant.
Alternatively, the organic contaminants include one or more of organic dye-based contaminants, antibiotic-based contaminants, organic pesticide-based contaminants, food additive-based contaminants, and by way of example, the organic contaminants may be rhodamine B, methylene blue, methyl blue, malachite green, orange G, sulfanilamide, tetracycline, oxytetracycline, carbamazepine, bisphenol a, parachlorophenol, phenol, 2,4, 6-trichlorophenol, aniline, and the like. Therefore, the sub-nano metal catalyst can be applied to various organic pollutants for catalyzing the decomposition of the peroxymonosulfate, and has wide application range, so that the sub-nano metal catalyst has wide application prospect.
The technical scheme of the present application will be further described with reference to examples and drawings.
Example 1
The embodiment of the invention discloses a preparation method of a sub-nanometer metal catalyst, which comprises the following steps:
phenolic acid compound dispersion: adding 0.2g of gallic acid into 40mL of ethanol, performing ultrasonic dispersion for 5min, heating to 80 ℃, and stirring at 500rpm for 30min to obtain phenolic acid compound suspension;
dispersing a transition metal compound: to 10mL of ethanol was added 0.1g Co (NO) 3 ) 2 ·6H 2 O, dispersing with ultrasonic for 3min, stirring at 500rpm at room temperature for 5min to obtain transition metal compound solution A liquid;
mixing: slowly and completely adding the transition metal compound solution into the phenolic acid compound suspension, performing ultrasonic dispersion for 3min, and then stirring at room temperature for 30min at a rotation speed of 500rpm to obtain a metal-phenolic acid complex solution;
doping: weighing 4g of cyanuric acid, adding the cyanuric acid into a metal-phenolic acid complex solution, heating to 70 ℃, stirring at 500rpm until the solvent is completely volatilized, and then drying in an oven at 75 ℃ for 8 hours to obtain a metal precursor mixture;
grinding: grinding the metal precursor mixture for 30min by a planetary ball mill at a rotating speed of 300rpm to obtain uniform and fine powder of the metal precursor mixture;
calcining: weighing powder of a certain amount of metal precursor mixture, putting the powder in a quartz boat, covering a cover, heating to 800 ℃ at a speed of 5 ℃/min in a tube furnace under nitrogen atmosphere, calcining for 2 hours, and naturally cooling to room temperature to obtain the sub-nano cobalt catalyst;
washing: washing the sub-nano cobalt catalyst with ethanol for 2-3 times to remove impurities, drying at 60 ℃ for 12 hours, and grinding with a mortar to obtain the sulfur-nitrogen co-doped carbon-loaded sub-nano cobalt catalyst.
The embodiment also discloses an application method of the sub-nanometer metal catalyst, which comprises the following steps:
100mL of a 0.1mM p-chlorophenol (4-CP) solution was added to a 250mL glass beaker, and the glass beaker was placed on a magnetic stirrer and stirred at a speed of 500 rpm;
weighing 2mg of the sub-nano cobalt catalyst by using an analytical balance, adding the sub-nano cobalt catalyst into the parachlorophenol solution, carrying out ultrasonic treatment for 3min to uniformly disperse the sub-nano cobalt catalyst, and stirring for 30min to enable the sub-nano cobalt catalyst and parachlorophenol molecules to reach an adsorption-desorption equilibrium state;
adding 15.4mg of peroxymonosulfate powder into the mixed solution of the sub-nanometer cobalt catalyst and the parachlorophenol to start oxidative degradation reaction, taking out 1mL of the reacted solution at a preset time point, and adding 1mL of methanol to terminate the reaction;
the residual concentration of parachlorophenol in the reacted solution was measured by high performance liquid chromatography after filtering to determine the removal effect.
As shown in fig. 1, fig. 1 is a representation diagram of a sub-nano cobalt catalyst, wherein fig. 1a is a scanning electron microscope image of the sub-nano cobalt catalyst, the sub-nano cobalt catalyst can be seen to be a curled porous sheet structure with many folds, fig. 1b is a transmission electron microscope image of the sub-nano cobalt catalyst, the sub-nano cobalt catalyst can be further judged to be a porous sheet structure from fig. 1b, fig. 1c is a high resolution transmission electron microscope image of the sub-nano cobalt catalyst, no obvious cobalt nano particles are observed from fig. 1c, fig. 1d is a low resolution high angle annular dark field scanning transmission electron microscope (HAADF-STEM) image of the sub-nano cobalt catalyst, no obvious cobalt particles are found from fig. 1d, which indicates that metal cobalt can be uniformly anchored on a carbon carrier in an extremely small size, fig. 1e is a transmission electron microscope adf-STEM image of the sub-nano cobalt catalyst corrected in a spherical aberration, as seen from fig. 1e, metal cobalt is uniformly distributed in a cluster form of ultra-small atoms and no metal clusters exist between carbon particles of 0.3nm and no nano particles exist between carbon particles.
Referring to fig. 2, fig. 2a shows an X-ray diffraction pattern of a sub-nano cobalt catalyst, as shown in fig. 2a, only a peak of graphite carbon is shown on the diffraction pattern, and no peak belonging to cobalt nanoparticles appears, which indicates that metallic cobalt in the sub-nano cobalt catalyst is supported on a carbon carrier in a single atom or amorphous state, fig. 2b shows an X-ray photoelectron spectrum of the sub-nano cobalt catalyst, which further proves that cobalt is indeed doped into the sub-nano cobalt catalyst, fig. 2c and 2d show a nitrogen adsorption-desorption isothermal diagram and a pore size distribution diagram of the sub-nano cobalt catalyst, respectively, as shown in fig. 2c and 2d, the sub-nano cobalt catalyst has a higher specific surface area and a graded porous structure, which is beneficial to mass transfer in the reaction process, and is proved to be very suitable for catalytic application.
In summary, the preparation method provided in the first embodiment successfully synthesizes the carbon-supported sub-nano cobalt catalyst, and the carbon-supported sub-nano cobalt has smaller particle size and good dispersibility, so that the catalyst has excellent catalytic activity.
As shown in FIG. 3, FIG. 3 is a graph showing the dissolution of cobalt ions when the sub-nanometer cobalt catalyst catalyzes the oxidative degradation of p-chlorophenol by peroxymonosulfate, and the result shows that the dissolution of cobalt ions is less than 50 MugL after 6h of reaction -1 Proved by the fact, the sub-nanometer cobalt catalyst has extremely high stability, and can effectively avoid the dissolution of cobalt metal in the reaction process.
Further, the recycling property of the sub-nano cobalt catalyst for degrading the parachlorophenol by activating the peroxymonosulfate is researched by controlling the reaction time to be unchanged (15 min), the sub-nano cobalt catalyst after the reaction is washed by methanol and deionized water before being repeatedly used and then is put into the next round of reaction, and the result is shown in fig. 4, the sub-nano cobalt catalyst still has higher catalytic activity after being repeatedly used for 5 times, and the removal rate of the reaction system to the parachlorophenol is still more than 96%, so that the sub-nano cobalt catalyst has good recycling property.
Example two
The second embodiment of the invention discloses a preparation method of a sub-nanometer metal catalyst, which is different from the first embodiment in that the transition metal compound is Fe (NO) 3 ) 3 ·9H 2 O, in other words, co (NO) in the transition metal compound dispersing step 3 ) 2 ·6H 2 O is replaced by Fe (NO) 3 ) 3 ·9H 2 O, namely, the sub-nano metal catalyst prepared in the second embodiment of the invention is a sub-nano iron catalyst.
The second embodiment of the invention also discloses an application method of the sub-nanometer metal catalyst, which is different from the first embodiment in that the sub-nanometer metal catalyst is the sub-nanometer iron catalyst prepared in the second embodiment of the invention.
Example III
The third embodiment of the invention discloses a preparation method of a sub-nanometer metal catalyst, which is different from the first embodiment in that the transition metal compound is Ni (NO) 3 ) 2 ·6H 2 O, in other words, co (NO) in the transition metal compound dispersing step 3 ) 2 ·6H 2 O is replaced by Ni (NO) 3 ) 2 ·6H 2 O, namely, the sub-nano metal catalyst prepared in the third embodiment of the invention is a sub-nano nickel catalyst.
The third embodiment of the invention also discloses an application method of the sub-nano metal catalyst, which is different from the application method of the sub-nano metal catalyst in the first embodiment in that the sub-nano metal catalyst is the sub-nano nickel catalyst prepared in the third embodiment of the invention.
Example IV
The fourth embodiment of the invention discloses a preparation method of a sub-nanometer metal catalyst, which is different from the first embodiment in that the transition metal compound is Cu (NO) 3 ) 3 ·3H 2 O, in other words, co (NO) in the transition metal compound dispersing step 3 ) 2 ·6H 2 O is replaced by Cu (NO) 3 ) 3 ·3H 2 O, namely, the sub-nano metal catalyst prepared in the fourth embodiment of the invention is a sub-nano copper catalyst.
The fourth embodiment of the invention also discloses an application method of the sub-nanometer metal catalyst, which is different from the application method of the sub-nanometer metal catalyst in the first embodiment in that the sub-nanometer metal catalyst is the sub-nanometer copper catalyst prepared in the fourth embodiment of the invention.
Example five
The fifth embodiment of the invention discloses a preparation method of a sub-nanometer metal catalyst, which is different from the first embodiment in that the transition metal compound is Mn (NO) 3 ) 3 ·4H 2 O, in other words, co (NO) in the transition metal compound dispersing step 3 ) 2 ·6H 2 O is replaced by Mn (NO) 3 ) 3 ·4H 2 O, namely, the sub-nano metal catalyst prepared in the fifth embodiment of the invention is a sub-nano manganese catalyst.
The fifth embodiment of the invention also discloses an application method of the sub-nanometer metal catalyst, which is different from the first embodiment in that the sub-nanometer metal catalyst is the sub-nanometer manganese catalyst prepared in the fifth embodiment of the invention.
As shown in fig. 5 and 6, fig. 5 is an X-ray diffraction pattern of four kinds of sub-nano metal catalysts (sub-nano iron catalyst, sub-nano nickel catalyst, sub-nano copper catalyst, sub-nano manganese catalyst) prepared in the second to fourth embodiments, and fig. 6 a to d are HAADF-STEM patterns of spherical aberration correction of four kinds of sub-nano metal catalysts (sub-nano iron catalyst, sub-nano nickel catalyst, sub-nano copper catalyst, sub-nano manganese catalyst) prepared in the second to fourth embodiments, respectively. No peaks ascribed to metal nanoparticles are observed in fig. 5, and it is understood that all of the four metals (iron, copper, nickel, manganese) are dispersed on the carbon support in the form of sub-nanoparticles in conjunction with fig. 6.
Fig. 7 is a graph showing the efficacy of four sub-nano metal catalysts (sub-nano iron catalyst, sub-nano nickel catalyst, sub-nano copper catalyst, sub-nano manganese catalyst) prepared in examples two to four for catalyzing the degradation of peroxymonosulfate to remove p-chlorophenol. As can be seen from fig. 7, all of the four sub-nano metal catalysts show high performance of efficiently activating the degradation of peroxymonosulfate to remove p-chlorophenol, wherein the iron sub-nano catalyst shows optimal catalytic performance, and the removal rate of p-chlorophenol reaches 100% within 10min, which shows that the iron sub-nano catalyst has considerable advantages in the current sub-nano metal catalysts.
Example five
The fifth embodiment of the invention discloses a preparation method of a sub-nanometer metal catalyst, which comprises the following steps:
phenolic acid compound dispersion: adding 0.2g of gallic acid into 40mL of ethanol, performing ultrasonic dispersion for 5min, heating to 80 ℃, and stirring at 500rpm for 30min to obtain suspended phenolic acid compound suspension;
dispersing a transition metal compound: to 10mL of ethanol was added 0.05g Co (NO) 3 ) 2 ·6H 2 O, dispersing with ultrasonic for 3min, stirring at room temperature at 500rpm for 5min to obtain transition metal compound A solution of matter;
mixing: slowly and completely adding the transition metal compound solution into the phenolic acid compound suspension, performing ultrasonic dispersion for 3min, and then stirring at 500rpm for 30min at room temperature to obtain a metal-phenolic acid complex solution;
doping: weighing 4g of cyanuric acid, adding the cyanuric acid into a metal-phenolic acid complex solution, heating to 70 ℃, stirring at 500rpm until the solvent is completely volatilized, and then drying in an oven at 75 ℃ for 8 hours to obtain a metal precursor mixture;
grinding: grinding the metal precursor mixture for 30min by a planetary ball mill at a rotating speed of 300rpm to obtain uniform and fine powder of the metal precursor mixture;
calcining: weighing a certain amount of metal precursor powder, putting the powder into a quartz boat, covering a cover, heating to 700 ℃ at a speed of 5 ℃/min in a nitrogen atmosphere in a tube furnace, calcining for 2 hours, and naturally cooling to room temperature to obtain the sub-nano cobalt catalyst;
washing: washing the sub-nano cobalt catalyst with ethanol for 2-3 times to remove impurities, drying at 60 ℃ for 12 hours, and grinding with a mortar to obtain the sulfur-nitrogen co-doped carbon-loaded sub-nano cobalt catalyst.
The embodiment also discloses an application method of the sub-nanometer metal catalyst, which comprises the following steps:
100mL of a 0.1mM parachlorophenol solution was added to a 250mL glass beaker, and the glass beaker was placed on a magnetic stirrer and stirred at a speed of 500 rpm;
weighing 2mg of the sub-nano cobalt catalyst by using an analytical balance, adding the sub-nano cobalt catalyst into the parachlorophenol solution, carrying out ultrasonic treatment for 3min to uniformly disperse the sub-nano cobalt catalyst, and stirring for 30min to enable the sub-nano cobalt catalyst and parachlorophenol molecules to reach an adsorption-desorption equilibrium state;
adding 15.4mg of peroxymonosulfate powder into the mixed solution of the sub-nanometer cobalt catalyst and the parachlorophenol to start oxidative degradation reaction, taking out 1mL of the reacted solution at a preset time point, and adding 1mL of methanol to terminate the reaction;
the residual concentration of parachlorophenol in the reacted solution was measured by high performance liquid chromatography after filtering to determine the removal effect.
Example six
The sixth embodiment of the invention discloses a preparation method of a sub-nanometer metal catalyst, which comprises the following steps:
phenolic acid compound dispersion: adding 0.2g of gallic acid into 40mL of ethanol, performing ultrasonic dispersion for 5min, heating to 80 ℃, and stirring at 500rpm for 30min to obtain phenolic acid compound suspension;
dispersing a transition metal compound: to 10mL of ethanol was added 0.15g Co (NO) 3 ) 2 ·6H 2 O, performing ultrasonic dispersion for 3min, and stirring at room temperature at 500rpm for 5min to obtain a transition metal compound solution;
mixing: slowly and completely adding the transition metal compound solution into the phenolic acid compound suspension, performing ultrasonic dispersion for 3min, and then stirring at room temperature and 500rpm for 30min to obtain a metal-phenolic acid complex solution;
doping: weighing 4g of cyanuric acid, adding the cyanuric acid into a metal-phenolic acid complex solution, heating to 70 ℃, stirring at 500rpm until the solvent is completely volatilized, and then drying in an oven at 75 ℃ for 8 hours to obtain a metal precursor mixture;
grinding: grinding the step metal precursor mixture for 30min by a planetary ball mill at a rotating speed of 300rpm to obtain uniform and fine powder of the metal precursor mixture;
calcining: weighing powder of a certain amount of metal precursor mixture, putting the powder in a quartz boat, covering a cover, heating to 700 ℃ at a speed of 10 ℃/min in a tube furnace under nitrogen atmosphere, calcining for 2 hours, and naturally cooling to room temperature to obtain the sub-nano cobalt catalyst;
washing: washing the sub-nano cobalt catalyst with ethanol for 2-3 times to remove impurities, drying at 60 ℃ for 12 hours, and grinding with a mortar to obtain the sulfur-nitrogen co-doped carbon-loaded sub-nano cobalt catalyst.
The embodiment also discloses an application method of the sub-nanometer metal catalyst, which comprises the following steps:
100mL of a 0.1mM parachlorophenol solution was added to a 250mL glass beaker, and the glass beaker was placed on a magnetic stirrer and stirred at a speed of 500 rpm;
weighing 2mg of the sub-nano cobalt catalyst by using an analytical balance, adding the sub-nano cobalt catalyst into the parachlorophenol solution, carrying out ultrasonic treatment for 3min to uniformly disperse the sub-nano cobalt catalyst, and stirring for 30min to enable the sub-nano cobalt catalyst and parachlorophenol molecules to reach an adsorption-desorption equilibrium state;
adding 15.4mg of peroxymonosulfate powder into the mixed solution of the sub-nanometer cobalt catalyst and the parachlorophenol to start oxidative degradation reaction, taking out 1mL of the reacted solution at a preset time point, and adding 1mL of methanol to terminate the reaction;
the residual concentration of parachlorophenol in the reacted solution was measured by high performance liquid chromatography after filtering to determine the removal effect.
Comparative example one
The first comparative example of the present invention discloses a preparation method of a sub-nano metal catalyst, which is different from the preparation method of the sub-nano metal catalyst of the first embodiment in that the preparation method omits the step of dispersing phenolic acid compounds, i.e. gallic acid is not added.
As shown in fig. 8, fig. 8 is a transmission electron microscope image of the sub-nano metal catalyst prepared in the first comparative example, and as can be seen from fig. 8, obvious cobalt nano particles appear on the surface of the sub-nano metal catalyst, which indicates that the metal particles further grow up under the condition of not adding gallic acid precursor, thereby confirming the key role of gallic acid in limiting the overgrowth of the metal particles.
Comparative example two
Comparative example two discloses a method of using a sub-nano metal catalyst, which is different from that of example one in that the physical adsorption of sub-nano cobalt catalyst alone adsorbs parachlorophenol without adding peroxymonosulfate.
Comparative example three
Comparative example three discloses a method of decomposing p-chlorophenol by peroxymonosulfate, which is different from the application method of the sub-nano metal catalyst in example one in that the sub-nano metal catalyst is not added, that is, the p-chlorophenol is decomposed by peroxymonosulfate alone.
As shown in fig. 9, fig. 9 shows the efficacy graphs of p-chlorophenol degradation in the first embodiment, the second embodiment and the third embodiment, and as can be seen from fig. 9, in the manner that the second embodiment does not add a sulfate but uses a sub-nano cobalt catalyst alone, the contribution ratio of adsorption of the sub-nano cobalt catalyst to removal of p-chlorophenol is negligible, in the manner that the third embodiment does not add the sub-nano cobalt catalyst but only degrades p-chlorophenol through a persulfate, the sub-nano cobalt catalyst does not automatically decompose to generate active species to cause removal of p-chlorophenol, and in the manner of the first embodiment, that is, both the sub-nano cobalt catalyst and the persulfate are added into the p-chlorophenol solution to degrade p-chlorophenol, the removal phenomenon of p-chlorophenol obviously occurs, and the above results indicate that the sub-nano cobalt catalyst can efficiently activate the persulfate to degrade to remove p-chlorophenol.
Comparative example four
Comparative example four discloses a method for preparing a nano metal catalyst, which is different from the method for preparing a sub-nano metal catalyst of example one in that 4g of cyanuric acid in the doping step is replaced with 2.7g of melamine to prepare a nano cobalt catalyst.
The fourth comparative example also discloses a preparation method of the nano metal catalyst prepared by the method, which is different from the application method of the sub-nano metal catalyst in the embodiment in that the sub-nano cobalt catalyst is replaced by the nano cobalt catalyst prepared in the embodiment.
As shown in fig. 10, fig. 10 is a graph showing the performance comparison of the sub-nano cobalt catalyst in the first embodiment and the cobalt nano catalyst in the fourth embodiment, and as can be seen from fig. 10, the reaction efficiency of the sub-nano cobalt catalyst for catalyzing the degradation of parachlorophenol by peroxymonosulfate is significantly higher than that of the cobalt nano catalyst. Therefore, the sub-nano cobalt catalyst obtained by the preparation method provided in the embodiment I has excellent activity and stability in the process of activating the peroxymonosulfate to degrade organic pollutants.
The sub-nano metal catalyst disclosed in the embodiment of the invention, the preparation method and the application method thereof are described in detail, and specific examples are applied to illustrate the principle and the implementation mode of the invention, and the description of the above examples is only used for helping to understand the sub-nano metal catalyst, the preparation method, the application method and the core idea of the invention; meanwhile, as those skilled in the art will vary in the specific embodiments and application scope according to the idea of the present invention, the present disclosure should not be construed as limiting the present invention in summary.
Claims (11)
1. A method for preparing a sub-nano metal catalyst, which is characterized by comprising the following steps:
complexing: dispersing phenolic acid compounds and transition metal compounds in a first solvent to form a metal-phenolic acid complex solution;
doping: adding a nitrogen-containing sulfur source into the metal-phenolic acid complex solution, stirring at 50-100 ℃ until the first solvent volatilizes, and drying to obtain a metal precursor mixture;
calcining: calcining the metal precursor mixture in a protective gas atmosphere, and cooling to room temperature to obtain the sub-nano metal catalyst, wherein the calcining temperature is 650-1050 ℃ and the calcining time is 0.5-3 h.
2. The method for preparing a sub-nano metal catalyst according to claim 1, wherein the complexing step is:
phenolic acid compound dispersion: dispersing the phenolic acid compound in a second solvent to form a phenolic acid compound suspension;
dispersing a transition metal compound: dispersing the transition metal compound in a third solvent to form a transition metal compound solution;
mixing: the transition metal compound solution and the transition metal compound solution are uniformly mixed to form the metal-phenolic acid complex solution.
3. The method of preparing a sub-nano metal catalyst according to claim 1, wherein prior to the calcining step, the preparing method further comprises:
grinding: the metal precursor mixture is ground to a powder.
4. The method of preparing a sub-nano metal catalyst according to claim 1, wherein the step of calcining is:
and heating the metal precursor mixture to 650-1050 ℃ at a heating rate of 1-15 ℃/min under the protective gas atmosphere, calcining, and cooling to room temperature to obtain the sub-nano metal catalyst.
5. The method of preparing a sub-nano metal catalyst according to claim 1, wherein after the step of calcining, the method of preparing further comprises:
washing: washing the sub-nano metal catalyst with a fourth solvent to remove impurities of the sub-nano metal catalyst, and drying and grinding to form the powdery sub-nano metal catalyst.
6. The method for preparing a sub-nano metal catalyst according to any one of claim 1 to 5, wherein,
the phenolic acid compound comprises one or more of gallic acid, chlorogenic acid, gallic acid, ferulic acid and mesonic acid;
The transition metal element in the transition metal compound comprises one or more of iron element, cobalt element, nickel element, copper element and manganese element;
the nitrogen-sulfur-containing source comprises one or more of cyanuric acid, thiocyanic acid, thiourea and thioacetamide.
7. The method for preparing a sub-nano metal catalyst according to any one of claim 1 to 5, wherein,
the mass ratio of the transition metal compound to the phenolic acid compound is 1:1-1:10; and/or the number of the groups of groups,
the mass ratio of the nitrogen-containing sulfur source to the phenolic acid compound is 1:10-1:30.
8. A sub-nano metal catalyst, which is characterized in that the sub-nano metal catalyst is prepared by the preparation method of the sub-nano metal catalyst according to any one of claims 1 to 7, and the sub-nano metal catalyst is a sulfur-nitrogen co-doped carbon-based sub-nano catalyst loaded with transition metal.
9. A method of using the sub-nano metal catalyst according to claim 8, wherein the method of using comprises:
dispersing the sub-nano metal catalyst in wastewater containing organic pollutants, stirring until the sub-nano metal catalyst and the organic pollutants reach an adsorption-desorption equilibrium state, and adding peroxymonosulfate to decompose the organic pollutants, wherein the transition metal elements in the sub-nano metal catalyst comprise: one or more of cobalt element, iron element, nickel element, manganese element and copper element.
10. The method for using a sub-nano metal catalyst according to claim 9, wherein the pH of the wastewater is 2-14, and/or,
the organic pollutants comprise one or more of organic dye pollutants, antibiotic pollutants, organic pesticide pollutants and food additive pollutants.
11. The method for using a sub-nano metal catalyst according to claim 9, wherein the mass ratio of the sub-nano metal catalyst to the peroxymonosulfate is 200:317-20:317; and/or the number of the groups of groups,
the molar ratio of the organic pollutant to the peroxymonosulfate is 1:1-20:1.
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