CN117443421A - Sulfur and nitrogen co-doped carbon-supported transition metal monoatomic catalyst, and preparation method and application thereof - Google Patents
Sulfur and nitrogen co-doped carbon-supported transition metal monoatomic catalyst, and preparation method and application thereof Download PDFInfo
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- CN117443421A CN117443421A CN202311327674.8A CN202311327674A CN117443421A CN 117443421 A CN117443421 A CN 117443421A CN 202311327674 A CN202311327674 A CN 202311327674A CN 117443421 A CN117443421 A CN 117443421A
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- Prior art keywords
- nitrogen
- transition metal
- sulfur
- doped carbon
- supported transition
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 79
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 73
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 49
- 239000011593 sulfur Substances 0.000 title claims abstract description 47
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 19
- -1 transition metal salt Chemical class 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 7
- 238000002791 soaking Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 claims description 25
- 229910017052 cobalt Inorganic materials 0.000 claims description 16
- 239000010941 cobalt Substances 0.000 claims description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 15
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- 238000006731 degradation reaction Methods 0.000 claims description 12
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 12
- 230000015556 catabolic process Effects 0.000 claims description 11
- 239000002957 persistent organic pollutant Substances 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims description 6
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 claims description 6
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 6
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims description 6
- 229940116357 potassium thiocyanate Drugs 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 3
- 239000001263 FEMA 3042 Substances 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 3
- 239000000446 fuel Substances 0.000 claims description 3
- 229940074391 gallic acid Drugs 0.000 claims description 3
- 235000004515 gallic acid Nutrition 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 3
- 235000015523 tannic acid Nutrition 0.000 claims description 3
- 229940033123 tannic acid Drugs 0.000 claims description 3
- 229920002258 tannic acid Polymers 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- INDBQWVYFLTCFF-UHFFFAOYSA-L cobalt(2+);dithiocyanate Chemical compound [Co+2].[S-]C#N.[S-]C#N INDBQWVYFLTCFF-UHFFFAOYSA-L 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 229940079877 pyrogallol Drugs 0.000 claims 2
- 230000004913 activation Effects 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 239000002105 nanoparticle Substances 0.000 description 8
- 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 7
- 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 7
- 229940043267 rhodamine b Drugs 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000002386 leaching Methods 0.000 description 5
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- 229910002514 Co–Co Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013310 covalent-organic framework Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
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- 230000007935 neutral effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 2
- 230000005469 synchrotron radiation Effects 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- GPKIXZRJUHCCKX-UHFFFAOYSA-N 2-[(5-methyl-2-propan-2-ylphenoxy)methyl]oxirane Chemical compound CC(C)C1=CC=C(C)C=C1OCC1OC1 GPKIXZRJUHCCKX-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 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
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 239000000975 dye Substances 0.000 description 1
- 231100000049 endocrine disruptor Toxicity 0.000 description 1
- 239000000598 endocrine disruptor Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 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
- 229910021645 metal ion Inorganic materials 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- UKDHSAZUXNLNLV-UHFFFAOYSA-N nickel(2+) dinitrate tetrahydrate Chemical compound O.O.O.O.[Ni++].[O-][N+]([O-])=O.[O-][N+]([O-])=O UKDHSAZUXNLNLV-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229960005404 sulfamethoxazole Drugs 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Thermal Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of monoatomic catalysts, and discloses a sulfur and nitrogen co-doped carbon-supported transition metal monoatomic catalyst, a preparation method and application thereof. The preparation method comprises the following steps: and mixing and stirring the transition metal salt, the carbon source powder, the nitrogen source powder and the sulfur source powder uniformly, and calcining under the protection of inert gas, cooling, optionally soaking in dilute acid, optionally washing with water and optionally drying to obtain the sulfur and nitrogen co-doped carbon-loaded transition metal monoatomic catalyst. The method is simple and convenient; the raw materials are low in cost; the prepared catalyst has high activation efficiency on the peroxymonosulfate, is environment-friendly, and has no pollution risk.
Description
Technical Field
The invention belongs to the technical field of monoatomic catalysts, and particularly relates to a sulfur and nitrogen co-doped carbon-supported transition metal monoatomic catalyst, a preparation method and application thereof.
Background
Peroxomonosulfate (PMS) is one of the advanced oxidation techniques that can effectively degrade organic pollutants. At room temperature, peroxymonosulfate is very stable and cannot directly degrade organic pollutants, and the peroxygen bond (O-O) in the molecule of peroxymonosulfate needs to be activated through a catalyst to generate hydroxyl groups (OH) and sulfate groups (SO) - 4 ) Free radical or singlet oxygen 1 O 2 ) Or degrading organic contaminants in a non-radical way. Carbon-based catalysts are receiving increasing attention for their good electrical conductivity, large specific surface area, stability and low cost. The high-efficiency carbon-based catalyst generally contains transition metals such as iron, cobalt, manganese and the like, takes the transition metals as catalytic centers, and forms an unsaturated coordination structure with nitrogen to be supported on a carbon substrate, so as to form a structure of M (metal) -N (biogen) -C (carbon). In recent years, single-atom catalysts have been widely used for pollutant degradation, fuel cells, and CO due to their ultra-high atom utilization, unsaturated coordination structures, and uniform distribution of active centers 2 Reduction and other catalytic reactions have become hot spots in current research.
Increasing the number of monoatomic active sites per unit volume and regulating the electronic coordination structure of the active sites are two general strategies to further increase the catalytic activity of monoatomic catalysts. At present, related researches show that the doping of nonmetallic atoms (such as nitrogen, boron, sulfur and phosphorus) can regulate and control the coordination electronic structure of the single-atom active center, thereby being beneficial to improving the activation efficiency of the activator. Oxygen doped, boron doped transition metal monoatomic catalysts have been reported. In contrast, sulfur doping has been reported to regulate the coordination structure of the active center of metal monoatomic catalysts.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art, and provides a sulfur and nitrogen co-doped carbon-supported transition metal monoatomic catalyst, a preparation method and application thereof. The method is simple and convenient; the raw materials are low in cost; the prepared catalyst has high activation efficiency on the peroxymonosulfate, is environment-friendly, and has no pollution risk.
In order to achieve the above object, the first aspect of the present invention provides a method for preparing a sulfur-nitrogen co-doped carbon-supported transition metal monoatomic catalyst, the method comprising: and mixing and stirring the transition metal salt, the carbon source powder, the nitrogen source powder and the sulfur source powder uniformly, and calcining under the protection of inert gas, cooling, optionally soaking in dilute acid, optionally washing with water and optionally drying to obtain the sulfur and nitrogen co-doped carbon-loaded transition metal monoatomic catalyst.
In the invention, transition metal salt is used as a metal monoatomic source, compounds containing carbon, nitrogen and sulfur are used as carbon sources, nitrogen sources and sulfur sources, and the sulfur and nitrogen co-doped carbon-supported transition metal monoatomic catalyst is obtained through high-temperature carbonization and is used for the activation of peroxymonosulfate. The catalyst changes the electron coordination structure of the single atom active center of the transition metal due to the doping of sulfur, enhances the catalytic activity and stability of the catalyst, and can also improve the density of the single atom of the transition metal. The peroxymonosulfate activated by the catalyst disclosed by the invention is mainly in a non-radical way of charge transfer, and can degrade various organic pollutants in water. And after the reaction, the leaching rate of metal ions in the solution is low, the biological safety risk is avoided, and the method is environment-friendly. The invention has great application prospect in the fields of environmental protection and pollutant control engineering.
According to the present invention, preferably, the content of the transition metal monoatoms is 0.01 to 2%, the content of the carbon is 65 to 75%, the content of the nitrogen is 15 to 30%, the content of the oxygen is 3 to 6%, and the content of the sulfur is 1 to 3% based on the total weight of the sulfur and nitrogen co-doped carbon supported transition metal monoatom catalyst.
According to the present invention, preferably, the density of the transition metal monoatoms in the sulfur-nitrogen co-doped carbon-supported transition metal monoatomic catalyst is determined by the content of the transition metal monoatoms; in the present invention, a sulfur and nitrogen co-doped carbon supported cobalt monoatomic catalyst is taken as an example, and the density of cobalt monoatomic is measured by X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma mass spectrometry (ICP-MS) together. For the "monoatomic" determination, it was determined by the degree of dispersion of cobalt in the spherical aberration diagram of FIG. 2 (i.e., less than 0.1-0.2nm, consistent with the monoatomic size range (0.1-0.5 nm)). Furthermore, the present application also confirms that the sulfur and nitrogen Co-doped carbon-supported cobalt monoatomic catalyst prepared by the present invention is only cobalt monoatomic, and is not doped with cobalt nanoclusters or cobalt nanoparticles (both of which have Co-Co bonds that would be detected by the synchrotron radiation) in combination with the absence of cobalt-cobalt bonds (Co-Co bond) in the synchrotron radiation of fig. 3.
According to the present invention, preferably, the transition metal is at least one of iron, cobalt, nickel, copper and manganese;
the transition metal salt is at least one of hydrochloride, sulfate, thiocyanate and nitrate of transition metal.
According to the present invention, preferably, the carbon source powder is at least one of a benzene ring-containing phenolic compound, a nitrogen-containing heterocyclic compound, thiourea, thiocyanic acid, potassium thiocyanate, ammonium thiocyanate, melamine, dicyandiamide, and urea.
According to the present invention, preferably, the nitrogen source powder is at least one of nitrogen-containing heterocyclic compound, thiourea, thiocyanic acid, potassium thiocyanate, ammonium thiocyanate, melamine, dicyandiamide and urea.
According to the present invention, preferably, the sulfur source powder is at least one of sulfur powder, thiourea, thiocyanate, cobalt thiocyanate, potassium thiocyanate and ammonium thiocyanate.
According to the present invention, preferably, the benzene ring-containing phenolic compound is at least one of tannic acid, gallic acid, pyrogallic acid, catechol, and phloroglucinol, and derivatives thereof.
According to the present invention, preferably, the nitrogen-containing heterocyclic compound is at least one nitrogen-containing heterocyclic compound containing pyrazole, pyridine, pyrrole and derivatives thereof.
According to the present invention, preferably, the conditions for calcination under inert gas protection include: the inert gas is nitrogen and/or argon, the calcination temperature is 500-1200 ℃, and the calcination time is less than 5 hours.
In the present invention, the equipment used for calcination is a tube furnace.
According to the invention, preferably, the cooling is to 15-35 ℃.
According to the present invention, preferably, the dilute acid is at least one of dilute sulfuric acid, dilute hydrochloric acid and dilute nitric acid, and the concentration of the dilute acid is 0 to 5M, preferably 0.1 to 1.5M; soaking in dilute acid for 0-24 hr, preferably 6-16 hr. In the process of preparing the sulfur and nitrogen co-doped carbon-supported transition metal monoatomic catalyst, high addition amount of metal atoms are converged to synthesize nano clusters or nano particles, and the metal nano clusters and the nano particles are catalytically active and have lower activity than single atoms (specifically, the catalytic activity of the metal clusters or the nano particles with the same molar amount is lower than that of the metal monoatomic catalyst with the same molar amount). According to the invention, through dilute acid soaking treatment after calcination, metal nanoclusters and nano particles doped in the catalyst are removed, and only metal monoatoms are reserved. The monoatomic catalyst reported in the prior art with a metal content of 0.5% -12% is one type of monoatomic catalyst in which nanoparticles are mixed with metal monoatoms.
The second aspect of the invention provides the sulfur and nitrogen co-doped carbon-supported transition metal single-atom catalyst prepared by the preparation method of the sulfur and nitrogen co-doped carbon-supported transition metal single-atom catalyst.
The third aspect of the invention provides the sulfur-nitrogen CO-doped carbon-loaded transition metal monoatomic catalyst for degrading organic pollutants in water, fuel cells and CO 2 Use in at least one of the reduction.
Preferably, the application in degrading organic pollutants in water bodies comprises activating peroxymonosulfate by utilizing the sulfur and nitrogen co-doped carbon-supported transition metal monoatomic catalyst.
The beneficial effects of the technical scheme of the application are as follows:
1. the preparation method of the invention is simple and easy to operate, the sources of raw materials are wide and easy to obtain, and the cost is low. The invention does not need to form a single atom active site by constructing a Metal Organic Framework (MOF) or a Covalent Organic Framework (COF), and does not need to use coordination compounds such as phenanthroline, phthalocyanine, porphyrin and the like. Nor does the feedstock involve graphene and carbon nanotubes.
2. In the catalyst, the content of the transition metal monoatoms accounts for 0.01% -2%, the density of the transition metal monoatoms can be adjusted through the content of the transition metal monoatoms, and the purity is high.
3. The invention changes the coordination structure of metal monoatoms through sulfur doping, and improves the catalytic activity of the catalyst. The catalyst prepared by the invention has high activation efficiency and wide application range. The catalyst prepared by the invention can activate the peroxymonosulfate in the pH range of 0-14, so that degradation of most organic pollutants such as dyes, antibiotics, endocrine disruptors and the like is realized, and the slightly acidic environment promotes the degradation reaction process. Wherein the apparent rate constant of the catalyst-activated peroxymonosulfate in example 1 below for rhodamine B degradation can reach K app ＝-0.6898min -1 The method comprises the steps of carrying out a first treatment on the surface of the The normalized rate constant can reach K N ＝-22396min -1 g -2 。
4. The catalyst prepared by the invention is environment-friendly, has low metal leaching rate and does not generate environmental pollution risk; the invention can be applied to the field of environmental protection for treating organic pollutants in water bodies, and has extremely high application value.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The foregoing and other objects, features and advantages of the invention will be apparent from the following more particular descriptions of exemplary embodiments of the invention as illustrated in the accompanying drawings wherein like reference numbers generally represent like parts throughout the exemplary embodiments of the invention.
Fig. 1 shows an element distribution transmission electron microscope image of a sulfur and nitrogen co-doped carbon supported transition metal single-atom catalyst prepared by a preparation method of the sulfur and nitrogen co-doped carbon supported transition metal single-atom catalyst provided by the embodiment 1 of the invention (wherein, "a" represents a transmission electron microscope image of the embodiment 1, "b" represents a high-angle annular dark field scanning transmission electron microscope image of the embodiment 1, "c" represents a distribution of a carbon element on the embodiment 1 sample, "d" represents a distribution of a nitrogen element on the embodiment 1 sample, "e" represents a distribution of an oxygen element on the embodiment 1 sample, "f" represents a distribution of a cobalt element on the embodiment 1 sample, and "g" represents a distribution of a sulfur element on the embodiment 1 sample).
Fig. 2 shows a spherical aberration electron microscope image (white dot-shaped is cobalt monoatom) of the sulfur-nitrogen co-doped carbon-supported transition metal monoatomic catalyst prepared by the preparation method of the sulfur-nitrogen co-doped carbon-supported transition metal monoatomic catalyst provided by the embodiment 1-3. ( Wherein fig. 2 (a) is the catalyst of example 1; FIG. 2 (b) is the catalyst of example 2; FIG. 2 (c) is the catalyst of example 3 )
FIG. 3 shows an X-ray fine absorption spectrum of a sulfur-nitrogen Co-doped carbon-supported transition metal single-atom catalyst prepared by the preparation method of the sulfur-nitrogen Co-doped carbon-supported transition metal single-atom catalyst provided in examples 1 and 3 of the present invention (wherein, "Co Foil" is cobalt Foil, "CoO" is cobalt oxide, "Co 3 O 4 "CoPc" is cobalt phthalocyanine, and "Normalized x.mu.E" represents the (Normalized) X-ray absorption intensity, and "Energy" represents the Energy of the X-ray (in electron volts).
Fig. 4 shows a degradation chart ("C/C0" is used to indicate the effect (degradation rate) of catalytic degradation of pollutants and "Time" is used to indicate Time) of rhodamine B under different pH conditions of the sulfur-nitrogen co-doped carbon-supported transition metal monoatomic catalyst prepared by the preparation method of the sulfur-nitrogen co-doped carbon-supported transition metal monoatomic catalyst provided in the embodiment 1 of the present invention.
FIG. 5 shows degradation patterns of six organic pollutants of sulfur and nitrogen co-doped carbon-supported transition metal monoatomic catalyst prepared by the preparation method of the sulfur and nitrogen co-doped carbon-supported transition metal monoatomic catalyst provided in example 1 of the invention under the conditions of (15.4 mg (0.5 mM) of potassium persulfate, 2mg of catalyst, 100mL of solution volume of water, 3.2 pH of potassium persulfate and any one of the following organic pollutants) of rhodamine B (RhB, 25 mu M), 4-chlorophenol (4-CP, 80 mu M), benzoic acid (BA, 10 mu M), sulfamethoxazole (SMX, 10 mu M), methylene blue (MB, 10 mu M) and carbamazepine (CMPZ, 10 mu M).
FIG. 6 shows a degradation chart of a sulfur-nitrogen co-doped carbon-supported transition metal single-atom catalyst prepared by the preparation method of the sulfur-nitrogen co-doped carbon-supported transition metal single-atom catalyst provided in the embodiments 1-4 of the present invention on rhodamine B (RhB, 25 μm) under the condition that the catalyst volume is 100mL, the pH3.2, of a solution composed of water, potassium persulfate, the catalyst and rhodamine B.
FIG. 7 shows a degradation chart of a sulfur-nitrogen co-doped carbon-supported transition metal monoatomic catalyst prepared by the preparation method of the sulfur-nitrogen co-doped carbon-supported transition metal monoatomic catalyst provided in examples 1 and 5-7 of the invention on rhodamine B (RhB, 25 mu M) under the condition that the catalyst is 2mg, the volume of a solution consisting of water, potassium persulfate, the catalyst and rhodamine B is 100mL, and the pH is 3.2.
FIG. 8 shows a cobalt ion leaching graph of a sulfur-nitrogen Co-doped carbon-supported transition metal single-atom catalyst prepared by the preparation method of the sulfur-nitrogen Co-doped carbon-supported transition metal single-atom catalyst according to examples 1 to 4 of the present invention after activation of a peroxymonosulfate (wherein, "Co 2+ leaching concentration "represents cobalt ion leaching concentration).
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention are described below, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
Example 1
The embodiment provides a preparation method of a sulfur and nitrogen co-doped carbon-supported transition metal monoatomic catalyst, which comprises the following steps: 50mg of cobalt nitrate hexahydrate, 200mg of gallic acid and 4g of thiocyanate powder are weighed, mixed, added into 20mL of ethanol, stirred and dried at 80 ℃. The mixture was placed in a tube furnace, warmed from room temperature to 800 ℃ at 5 ℃/min, and incubated for 2h, nitrogen was purged during calcination. And naturally cooling to room temperature after the calcination is completed. The obtained black powder is soaked in 0.5M dilute sulfuric acid for 12 hours, then washed to be neutral, and dried in vacuum, so that the sulfur and nitrogen co-doped carbon-supported transition metal monoatomic catalyst is obtained.
Example 2
The present embodiment provides a method for preparing a sulfur and nitrogen co-doped carbon supported transition metal monoatomic catalyst, which is different from embodiment 1 only in that: cobalt nitrate hexahydrate was 10mg.
Example 3
The present embodiment provides a method for preparing a sulfur and nitrogen co-doped carbon supported transition metal monoatomic catalyst, which is different from embodiment 1 only in that: cobalt nitrate hexahydrate was 100mg.
Example 4
The embodiment provides a preparation method of a sulfur and nitrogen co-doped carbon-supported transition metal monoatomic catalyst, which comprises the following steps: 25mg of cobalt nitrate hexahydrate, 200mg of tannic acid and 8g of thiourea powder are weighed, mixed, milled for 20min, the mixture is placed in a tube furnace, the temperature is raised from room temperature to 850 ℃ at 10 ℃/min, the temperature is kept for 2h, and nitrogen is introduced for protection during calcination. And naturally cooling to room temperature after the calcination is completed. The obtained black powder is soaked in 1M dilute sulfuric acid for 12 hours, then washed to be neutral, and dried in vacuum, so that the sulfur and nitrogen co-doped carbon-supported transition metal monoatomic catalyst is obtained.
Example 5
The present embodiment provides a method for preparing a sulfur and nitrogen co-doped carbon supported transition metal monoatomic catalyst, which is different from embodiment 1 only in that: 50mg of cobalt nitrate hexahydrate was replaced with 50mg of ferric nitrate nonahydrate.
Example 6
The present embodiment provides a method for preparing a sulfur and nitrogen co-doped carbon supported transition metal monoatomic catalyst, which is different from embodiment 1 only in that: 50mg of cobalt nitrate hexahydrate was replaced with 50mg of nickel nitrate tetrahydrate.
Example 7
The present embodiment provides a method for preparing a sulfur and nitrogen co-doped carbon supported transition metal monoatomic catalyst, which is different from embodiment 1 only in that: 50mg of cobalt nitrate hexahydrate was replaced with 50mg of copper sulfate pentahydrate.
As can be seen from fig. 1, all five elements of carbon, nitrogen, oxygen, sulfur and cobalt can be uniformly distributed inside the final catalyst of example 1, and no visible cobalt nanoparticles are present.
As is clear from FIG. 2, the particle diameters of the cobalt monoatoms in examples 1 to 3 were all 0.1nm or less, and the scope of the monoatoms was reached. FIG. 2 (a) -example 1 shows a high single atom density and a uniform distribution (indicated by white dots); FIG. 2 (b) -example 2 shows a reduction in monoatomic density; FIG. 2 (c) -example 3 shows a high monoatomic density, but nanoclusters are locally present.
As can be seen from the differences in the spectral lines of fig. 3, examples 1, 3 are significantly different from the presence of cobalt Foil (Co Foil), without Co-Co bonds, excluding the presence of cobalt nanoparticles. At the same time, the curves of examples 1, 3 were obtained with cobalt oxide (CoO), tricobalt tetraoxide (Co 3 O 4 ) Cobalt phthalocyanine (CoPc) also differs, indicating the unique coordination structure of the Co monatomic active centers of examples 1 and 3.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described.
Claims (10)
1. A preparation method of a sulfur and nitrogen co-doped carbon-supported transition metal monoatomic catalyst, which is characterized by comprising the following steps: and mixing and stirring the transition metal salt, the carbon source powder, the nitrogen source powder and the sulfur source powder uniformly, and calcining under the protection of inert gas, cooling, optionally soaking in dilute acid, optionally washing with water and optionally drying to obtain the sulfur and nitrogen co-doped carbon-loaded transition metal monoatomic catalyst.
2. The method for preparing a sulfur-nitrogen co-doped carbon supported transition metal monoatomic catalyst according to claim 1, wherein the content of transition metal monoatomic is 0.01 to 2%, the content of carbon is 65 to 75%, the content of nitrogen is 15 to 30%, the content of oxygen is 3 to 6%, and the content of sulfur is 1 to 3% based on the total weight of the sulfur-nitrogen co-doped carbon supported transition metal monoatomic catalyst.
3. The method for preparing a sulfur-nitrogen co-doped carbon supported transition metal monoatomic catalyst according to claim 2, wherein the density of transition metal monoatoms in the sulfur-nitrogen co-doped carbon supported transition metal monoatomic catalyst is determined by the content of the transition metal monoatoms.
4. The method for preparing a sulfur-nitrogen co-doped carbon supported transition metal monoatomic catalyst according to claim 1, wherein the transition metal is at least one of iron, cobalt, nickel, copper and manganese;
the transition metal salt is at least one of hydrochloride, sulfate, thiocyanate and nitrate of transition metal.
5. The method for preparing the sulfur-nitrogen co-doped carbon-supported transition metal monoatomic catalyst according to claim 1, wherein,
the carbon source powder is at least one of phenol compound containing benzene ring, nitrogen-containing heterocyclic compound, thiourea, thiocyanic acid, potassium thiocyanate, ammonium thiocyanate, melamine, dicyandiamide and urea;
the nitrogen source powder is at least one of nitrogen-containing heterocyclic compound, thiourea, thiocyanate, potassium thiocyanate, ammonium thiocyanate, melamine, dicyandiamide and urea;
the sulfur source powder is at least one of sulfur powder, thiourea, thiocyanate, cobalt thiocyanate, potassium thiocyanate and ammonium thiocyanate.
6. The method for preparing the sulfur-nitrogen co-doped carbon supported transition metal monoatomic catalyst according to claim 5, wherein,
the phenolic compound containing benzene ring is at least one of tannic acid, gallic acid, pyrogallol, catechol, pyrogallol and derivatives thereof;
the nitrogen-containing heterocyclic compound is at least one nitrogen-containing heterocyclic compound containing pyrazole, pyridine, pyrrole and derivatives thereof.
7. The method for preparing the sulfur-nitrogen co-doped carbon-supported transition metal monoatomic catalyst according to claim 1, wherein,
the conditions for calcination under inert gas protection include: the inert gas is nitrogen and/or argon, the calcining temperature is 500-1200 ℃, and the calcining time is less than 5 hours;
the cooling is to cool to 15-35 ℃;
the dilute acid is at least one of dilute sulfuric acid, dilute hydrochloric acid and dilute nitric acid, and the concentration of the dilute acid is 0-5M; soaking in dilute acid for 0-24h.
8. The sulfur-nitrogen co-doped carbon-supported transition metal monoatomic catalyst prepared by the method for preparing the sulfur-nitrogen co-doped carbon-supported transition metal monoatomic catalyst as claimed in any one of claims 1 to 7.
9. The sulfur, nitrogen CO-doped carbon supported transition metal monoatomic catalyst of claim 8 for degradation of organic pollutants in water, fuel cells and CO 2 Use in at least one of the reduction.
10. The use according to claim 9, wherein the use in the degradation of organic pollutants in water comprises activating peroxymonosulfate with the sulfur, nitrogen co-doped carbon supported transition metal monoatomic catalyst.
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