CN111420691B - Metal monoatomic catalyst and preparation method thereof - Google Patents
Metal monoatomic catalyst and preparation method thereof Download PDFInfo
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- CN111420691B CN111420691B CN202010202772.9A CN202010202772A CN111420691B CN 111420691 B CN111420691 B CN 111420691B CN 202010202772 A CN202010202772 A CN 202010202772A CN 111420691 B CN111420691 B CN 111420691B
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- Prior art keywords
- metal
- oxide
- monoatomic
- gas
- nitrogen
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 230
- 239000002184 metal Substances 0.000 title claims abstract description 229
- 239000003054 catalyst Substances 0.000 title claims abstract description 123
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 69
- 239000011259 mixed solution Substances 0.000 claims abstract description 66
- 239000000243 solution Substances 0.000 claims abstract description 57
- 239000002243 precursor Substances 0.000 claims abstract description 51
- 239000000758 substrate Substances 0.000 claims abstract description 44
- 239000007769 metal material Substances 0.000 claims abstract description 41
- 239000007789 gas Substances 0.000 claims abstract description 37
- -1 nitrogen-containing compound Chemical class 0.000 claims abstract description 28
- 239000002270 dispersing agent Substances 0.000 claims abstract description 22
- 238000005245 sintering Methods 0.000 claims abstract description 21
- 239000012298 atmosphere Substances 0.000 claims abstract description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000013532 laser treatment Methods 0.000 claims abstract description 14
- 230000001681 protective effect Effects 0.000 claims abstract description 14
- 238000011282 treatment Methods 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 125000004429 atom Chemical group 0.000 claims description 40
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 34
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 229910017052 cobalt Inorganic materials 0.000 claims description 16
- 239000010941 cobalt Substances 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 230000001678 irradiating effect Effects 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 9
- 239000003575 carbonaceous material Substances 0.000 claims description 9
- 150000004767 nitrides Chemical class 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 8
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 7
- 229940098691 coco monoethanolamide Drugs 0.000 claims description 7
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 7
- 239000001307 helium Substances 0.000 claims description 7
- 229910052734 helium Inorganic materials 0.000 claims description 7
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 229910052741 iridium Inorganic materials 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 239000010931 gold Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 6
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 6
- 239000012621 metal-organic framework Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 6
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 6
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- GWTCIAGIKURVBJ-UHFFFAOYSA-L dipotassium;dodecyl phosphate Chemical compound [K+].[K+].CCCCCCCCCCCCOP([O-])([O-])=O GWTCIAGIKURVBJ-UHFFFAOYSA-L 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 5
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 5
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229920002415 Pluronic P-123 Polymers 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 4
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052582 BN Inorganic materials 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005751 Copper oxide Substances 0.000 claims description 3
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims description 3
- 229910039444 MoC Inorganic materials 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 3
- 239000005083 Zinc sulfide Substances 0.000 claims description 3
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 3
- KSECJOPEZIAKMU-UHFFFAOYSA-N [S--].[S--].[S--].[S--].[S--].[V+5].[V+5] Chemical compound [S--].[S--].[S--].[S--].[S--].[V+5].[V+5] KSECJOPEZIAKMU-UHFFFAOYSA-N 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- SKKMWRVAJNPLFY-UHFFFAOYSA-N azanylidynevanadium Chemical compound [V]#N SKKMWRVAJNPLFY-UHFFFAOYSA-N 0.000 claims description 3
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 claims description 3
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 claims description 3
- 229910001567 cementite Inorganic materials 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- 229910000431 copper oxide Inorganic materials 0.000 claims description 3
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 3
- 229940079886 disodium lauryl sulfosuccinate Drugs 0.000 claims description 3
- KHIQYZGEUSTKSB-UHFFFAOYSA-L disodium;4-dodecoxy-4-oxo-3-sulfobutanoate Chemical compound [Na+].[Na+].CCCCCCCCCCCCOC(=O)C(S(O)(=O)=O)CC([O-])=O.CCCCCCCCCCCCOC(=O)C(S(O)(=O)=O)CC([O-])=O KHIQYZGEUSTKSB-UHFFFAOYSA-L 0.000 claims description 3
- TVACALAUIQMRDF-UHFFFAOYSA-N dodecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(O)=O TVACALAUIQMRDF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000457 iridium oxide Inorganic materials 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 3
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 3
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 3
- 229910001954 samarium oxide Inorganic materials 0.000 claims description 3
- 229940075630 samarium oxide Drugs 0.000 claims description 3
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 229910001923 silver oxide Inorganic materials 0.000 claims description 3
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims description 3
- NYPFJVOIAWPAAV-UHFFFAOYSA-N sulfanylideneniobium Chemical compound [Nb]=S NYPFJVOIAWPAAV-UHFFFAOYSA-N 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 claims description 3
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 3
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
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- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 32
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract 1
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- 238000012360 testing method Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 231100000331 toxic Toxicity 0.000 description 4
- 230000002588 toxic effect Effects 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
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- 238000001354 calcination Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- TZGPACAKMCUCKX-UHFFFAOYSA-N 2-hydroxyacetamide Chemical compound NC(=O)CO TZGPACAKMCUCKX-UHFFFAOYSA-N 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- 229910002514 Co–Co Inorganic materials 0.000 description 1
- 229910018643 Mn—Si Inorganic materials 0.000 description 1
- 241001274216 Naso Species 0.000 description 1
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Abstract
The invention belongs to the technical field of catalysts, and particularly relates to a preparation method of a metal monatomic catalyst, which comprises the following steps: performing laser treatment on a mixed solution containing a metal material and a dispersing agent in a first protective gas atmosphere to obtain a metal monoatomic mixed solution; mixing the metal monoatomic solution with a substrate material, and then carrying out hydrothermal reaction to obtain a precursor loaded with metal monoatomic ions; and mixing the precursor with a nitrogen-containing compound in a second protective gas atmosphere, and then sintering to obtain the nitrogen-doped metal monatomic catalyst. The preparation method of the metal monatomic catalyst can obtain the metal monatomic catalyst only through simple laser treatment, hydrothermal reaction and sintering treatment, realizes metal monatomic active site catalysis, improves the catalytic performance of the material, is simple and easy to operate, and is easy to realize industrial large-scale production and application.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a metal monatomic catalyst and a preparation method thereof.
Background
With the wide application of chemical products in human life, the development of industrial chemistry has increasingly important key effects on social and technological advances. The catalyst has the advantages of improving the chemical reaction rate, reducing the reaction cost, improving the yield, saving the reaction time and the like, so the catalyst is a core material of industrial chemistry. The metal monatomic catalyst is a catalyst which improves the catalytic activity by using a metal monatomic site, is high-efficiency and exerts the metal utilization rate to the maximum extent, and therefore, has the advantages of low cost, high catalytic activity and the like. The metal monoatomic catalyst does not exist in a metal valence state but exists to form a covalent bond of M-N-C or M-O with a base material, so the metal monoatomic catalyst exhibits high catalytic activity and high stability in strong acid, strong basicity, strong oxidation and strong reduction.
In recent years, professor Dodelet reports that N-M-C (wherein N, M, C represent nitrogen, transition metal and carbon element, respectively) catalyst has high catalytic activity in journal of "science" in 2009. FeO in the institute of billows, university union, until 2011 x The surface grows monoatomic Pt, and the catalyst Pt/FeO x Has very high CO oxidation catalytic activity, which is also the first proposed single atom concept. So far, the metal monoatomic catalyst is applied and broken through in the chemical field like the bamboo shoots in spring after rain. For example, li Yamama academy skillfully anchors metal monatomic through a ZIF-8, ZIF-67 precursor, and then carries out high-temperature carbonization to obtain the metal monatomic catalyst. The method for preparing the metal monatomic catalyst at present mainly comprises the following steps: preparing organic metal frame particles or metal precursors to adsorb metal oxides or porous carbon materials, and finally preparing the metal monatomic catalyst through high-temperature carbonization or high-temperature reduction. However, these preparation methods have disadvantages of long process flow, need to use toxic precursors and toxic solvents, single kind of monatomic metal, and the monatomic metal is easy to agglomerate and lose part of activity after long-term use, thereby making it impossible to produce high-efficiency monatomic metal catalysts on a large scale.
Disclosure of Invention
The invention aims to provide a preparation method of a metal monatomic catalyst, and aims to solve the technical problems that the preparation method of the metal monatomic catalyst is long in process, needs to use a toxic precursor and a toxic solvent, and is single in type of the prepared monatomic metal, poor in stability and the like.
Another object of the present invention is to provide a metal monoatomic catalyst.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a preparation method of a metal monatomic catalyst comprises the following steps:
performing laser treatment on a mixed solution containing a metal material and a dispersing agent in a first protective gas atmosphere to obtain a metal monoatomic mixed solution;
mixing the metal monoatomic mixed solution with a substrate material, and then carrying out hydrothermal reaction to obtain a precursor loaded with metal monoatomic;
and mixing the precursor with a nitrogen-containing compound in a second protective gas atmosphere, and then sintering to obtain the nitrogen-doped metal monatomic catalyst.
Preferably, the laser processing step includes: and irradiating the metal material in the mixed solution containing the metal material for 0.01 to 5 hours by adopting laser with the power of 30 to 1000 w.
Preferably, the content of the dispersant is 0.01 to 10% by mass based on 100% by mass of the mixed solution containing the metal material.
Preferably, the mass percentage of the metal monoatomic compound solution is 0.1-5%.
Preferably, the type of laser is selected from: at least one of far infrared laser, mid-infrared laser, near-infrared laser, visible laser, and near-ultraviolet laser.
Preferably, the metallic material is selected from: at least one metal simple substance of iron, cobalt, nickel, copper, manganese, platinum, palladium, gold, silver, ruthenium, iridium and tungsten, or an alloy formed by at least two metals of iron, cobalt, nickel, copper, manganese, platinum, palladium, gold, silver, ruthenium, iridium and tungsten.
Preferably, the solvent in the mixed solution is selected from: at least one of water, methanol, ethanol, acetone, dichloromethane, isopropanol, ethylene glycol, dimethyl sulfoxide and dimethylformamide.
Preferably, the dispersant is selected from: block polymer P127, block polymer P123, polyethylene oxide, polyethylene glycol, disodium lauryl sulfosuccinate, disodium cocomonoethanolamide sulfosuccinate, monolauryl phosphate, potassium monolauryl phosphate, lauryl alcohol ether phosphate, potassium lauryl alcohol ether phosphate, ammonium fatty alcohol polyoxyethylene ether sulfate, cocomonoethanolamide, and at least one of cocoethyleneglycolamide.
Preferably, the step of hydrothermal reaction comprises: and mixing the metal monoatomic mixed solution with a substrate material, and reacting for 0.5-72 hours in a high-pressure reaction kettle at the temperature of 80-200 ℃.
Preferably, the volume ratio of the metal monoatomic solution to the base material is (1.5 to 20): 1.
preferably, the substrate material is selected from: at least one of carbon material, carbide, sulfide, nitride and oxide.
Preferably, the carbon material is selected from: the carbon material comprises at least one of active carbon, a metal organic framework material ZIF-8, a metal organic framework material ZIF-67, a carbon nano tube, graphite and graphene.
Preferably, the carbide is selected from: at least one of tungsten carbide, titanium carbide, iron carbide and molybdenum carbide.
Preferably, the oxide is selected from: at least one of aluminum oxide, silicon oxide, titanium oxide, vanadium oxide, manganese oxide, cobalt oxide, nickel oxide, iron oxide, copper oxide, zinc oxide, niobium oxide, molybdenum oxide, ruthenium oxide, iridium oxide, silver oxide, cadmium oxide, lanthanum oxide, cerium oxide, and samarium oxide.
Preferably, the sulphide is selected from: at least one of iron sulfide, vanadium sulfide, nickel sulfide, cobalt sulfide, cadmium sulfide, niobium sulfide and zinc sulfide.
The nitride is selected from: at least one of titanium nitride, vanadium nitride, silicon nitride and boron nitride.
Preferably, the step of sintering treatment comprises: after the precursor and the nitrogen-containing compound are mixed, the temperature is raised to 400-1200 ℃ at the heating rate of 1-50 ℃/min, and the reaction is carried out for 0.5-72 hours.
Preferably, the mass ratio of the precursor to the nitrogen-containing compound is 1: (0.001-0.3).
Preferably, the nitrogen-containing compound is selected from: at least one of melamine, cyanuric acid, triethylamine, ammonium borate, ammonium bicarbonate, ammonium sulfate, ammonium chloride and ammonium nitrate.
Preferably, the first protective gas is selected from: at least one of nitrogen, argon, helium.
Preferably, the second shielding gas is selected from: at least one of nitrogen, argon, helium, hydrogen, ammonia, and methane.
Preferably, the content of metal monoatomic atoms in the nitrogen-doped metal monoatomic catalyst is 0.2-7%.
Accordingly, a metal monoatomic catalyst which is prepared by the above-mentioned method for preparing a metal monoatomic catalyst.
The invention provides a preparation method of a metal monatomic catalyst, which comprises the steps of carrying out laser treatment on a mixed solution containing a metal material and a dispersing agent, enabling the metal material to enter the solution in a monatomic form, then mixing the metal monatomic mixed solution with a substrate material, carrying out hydrothermal reaction, enabling metal monatomic to be loaded on the substrate material to obtain a precursor, mixing the precursor with a nitrogen-containing compound, and then carrying out sintering treatment, wherein the nitrogen-containing compound is subjected to thermal decomposition in a high-temperature sintering process, nitrogen atoms are doped into the substrate material to form chemical bonding with the metal monatomic, so that the metal monatomic is firmly anchored on the surface of the substrate material, the nitrogen-doped metal monatomic catalyst with stable bonding is obtained, and the metal monatomic is prevented from falling off, agglomeration and the like, so that the catalytic effect and the service life of the catalyst are ensured. The preparation method of the metal monatomic catalyst can obtain the metal monatomic catalyst only through simple laser treatment, hydrothermal reaction and sintering treatment, realizes metal monatomic active site catalysis, improves the catalytic performance of the material, is simple and easy to operate, and is easy to realize industrial large-scale production and application.
The metal monatomic catalyst provided by the invention is prepared by the method, the bonding stability of the metal monatomic and the substrate material is good, the content of the metal monatomic in the catalyst is 0.2% -7%, the metal monatomic activity is high, and the catalytic effect is good; and the catalyst is doped with nitrogen elements, so that the combination stability of metal single atoms and a substrate material can be improved, the conductivity of the catalyst can be improved, and the catalytic effect is further improved.
Drawings
FIG. 1 is a schematic view of laser treatment in a method for preparing a metal monoatomic catalyst according to an embodiment of the present invention.
FIG. 2 is a transmission electron micrograph of a metal monoatomic catalyst according to example 1 of the present invention.
FIG. 3 is a transmission electron microscope image of a metal monoatomic catalyst according to example 2 of the present invention.
FIG. 4 is a transmission electron micrograph of a metal monoatomic catalyst according to example 3 of the present invention.
FIG. 5 is a transmission electron micrograph of a metal monoatomic catalyst according to example 4 of the present invention.
Detailed Description
In order to make the objects, technical solutions and technical effects of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive step in connection with the embodiments of the present invention shall fall within the scope of protection of the present invention.
In the description of the present invention, it is to be understood that the terms "first", "second", and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or to imply that the number of technical features indicated are in fact significant. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The weight of the related components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight of each component, therefore, the proportional enlargement or reduction of the content of the related components according to the description of the embodiments of the present invention is within the scope disclosed in the description of the embodiments of the present invention. Specifically, the weight described in the description of the embodiment of the present invention may be a unit of mass known in the chemical industry field, such as μ g, mg, g, and kg.
The embodiment of the invention provides a preparation method of a metal monatomic catalyst, which comprises the following steps:
s10, carrying out laser treatment on a mixed solution containing a metal material and a dispersing agent in a first protective gas atmosphere to obtain a metal monoatomic mixed solution;
s20, mixing the metal monoatomic mixed solution with a substrate material, and then carrying out hydrothermal reaction to obtain a precursor loaded with metal monoatomic;
and S30, mixing the precursor with a nitrogen-containing compound in a second protective gas atmosphere, and then sintering to obtain the nitrogen-doped metal monatomic catalyst.
According to the preparation method of the metal monatomic catalyst provided by the embodiment of the invention, the mixed solution containing the metal material and the dispersing agent is subjected to laser treatment, so that the metal material enters the solution in a monatomic form, then the metal monatomic mixed solution is mixed with the substrate material and then subjected to hydrothermal reaction, so that the metal monatomic is loaded on the substrate material to obtain the precursor, then the precursor is mixed with the nitrogen-containing compound and then subjected to sintering treatment, the nitrogen-containing compound is subjected to thermal decomposition in the high-temperature sintering process, the nitrogen atoms are doped into the substrate material to form chemical bonding with the metal monatomic, so that the metal monatomic is more firmly anchored on the surface of the substrate material, the nitrogen-doped metal monatomic catalyst with stable bonding is obtained, and the metal monatomic is prevented from falling, agglomeration and the like, so that the catalytic effect and the service life of the catalyst are ensured. According to the preparation method of the metal monatomic catalyst, the metal monatomic catalyst can be obtained only through simple laser treatment, hydrothermal reaction and sintering treatment, the metal monatomic active site catalysis is realized, the catalytic performance of the material is improved, the operation is simple and easy, and the industrial large-scale production and application are easy to realize.
Specifically, in S10, the mixed solution containing the metal material and the dispersant is subjected to laser processing in the first protective gas atmosphere to obtain a metal monoatomic mixed solution. In the embodiment of the invention, in order to prevent metal oxidation, the mixed solution of the metal material is subjected to laser treatment under the atmosphere of protective gas such as nitrogen, argon, helium and the like, and the metal material is irradiated by laser to enable the metal to enter the mixed solution in a monoatomic form, so that the metal monoatomic mixed solution is formed.
In some embodiments, the step of laser processing comprises: irradiating the metal material in the mixed solution containing the metal material for 0.01 to 5 hours by adopting laser with the power of 30 to 1000 w. According to the embodiment of the invention, the metal material in the mixed solution containing the metal material is irradiated for 0.01-5 hours by adopting the laser with the power of 30-1000 w, so that the metal material enters the mixed solution in the form of single atoms, and the forming rate of the single atoms in the metal material can be reasonably adjusted by adjusting the laser power and the laser irradiation time, thereby adjusting the content of the metal single atoms in the mixed solution. If the laser power is too high, the metal material formed by the laser enters the mixed solution in a non-monatomic form such as a block form, and the monatomic metal cannot be formed; if the laser power is too low, the metal material cannot dissociate to form metal monoatomic atoms. If the laser irradiation time is too long, the concentration of metal monoatomic atoms in the mixed solution is too high, and the metal monoatomic atoms are easy to agglomerate and exist in the mixed solution in a non-monoatomic form, so that the activity of the prepared catalyst is reduced. In some embodiments, the power of the laser may be 30w, 50w, 100w, 200w, 500w, 800w, 1000w, or the like, and the irradiation time may be 0.01 hour, 0.1 hour, 0.5 hour, 1 hour, 1.5 hours, 2 hours, 3 hours, 4 hours, or 5 hours.
In some embodiments, the type of laser is selected from: at least one of far infrared laser, mid-infrared laser, near-infrared laser, visible laser, and near-ultraviolet laser. The specific type of the laser is not specifically limited in the embodiments of the present invention, and may be any laser type such as a far infrared laser, a mid-infrared laser, a near-infrared laser, a visible laser, a near-ultraviolet laser, and the like, as long as the laser power can reach 30w to 1000w to effectively excite the metal monoatomic atoms on the metal material.
In some embodiments, the metal monoatomic solution includes 0.1% to 5% of metal monoatomic atoms by mass. According to the embodiment of the invention, the mixed solution containing the metal material is subjected to laser treatment, so that the metal material enters the mixed solution in a monoatomic form after being excited by laser to form the mixed solution with the metal monoatomic content of 0.1-5%, and the mixed solution with the metal monoatomic content can effectively ensure the content of the metal monoatomic atom in the prepared metal monoatomic catalyst, thereby ensuring the activity of the catalyst. If the content of the metal monoatomic solution is too high, the metal monoatomic solution is easily agglomerated in the mixed solution, and reaction sites are reduced, thereby reducing the activity of the catalyst.
In some embodiments, the mixed solution includes a metal material, a solvent, and a dispersant. According to the embodiment of the invention, the metal material is placed in the mixed solution of the solvent and the dispersing agent, wherein the dispersing agent can adsorb metal single atoms released by the metal material excited by laser, and the metal single atoms are prevented from being agglomerated in the mixed solution to lose activity. In some embodiments, after the metal material is placed in the mixed solution of the solvent and the dispersing agent, excess inert gas is introduced to exhaust the active gas in the solution, so as to avoid the damage of the active gas to the metal material and the subsequent excited metal monoatomic atoms.
In some embodiments, the content of the dispersant is 0.01 to 10% based on 100% of the total mass of the mixed solution containing the metal material, and the content of the dispersant is effective to ensure that the metal monoatomic group stably exists in the mixed solution, prevent the metal monoatomic group from agglomerating and deactivating, and influence the subsequent mixed hydrothermal reaction of the metal monoatomic mixed solution and the substrate material if the content of the dispersant is too high.
In some embodiments, the metallic material is selected from: at least one metal simple substance of iron, cobalt, nickel, copper, manganese, platinum, palladium, gold, silver, ruthenium, iridium and tungsten, or an alloy formed by at least two metals of iron, cobalt, nickel, copper, manganese, platinum, palladium, gold, silver, ruthenium, iridium and tungsten. The metal monoatomic materials released by the metal materials adopted by the embodiment of the invention after laser excitation have better catalytic activity, and the prepared metal monoatomic catalyst has high activity and good stability.
In some embodiments, the solvent in the mixed solution is selected from: at least one of water, methanol, ethanol, acetone, dichloromethane, isopropanol, ethylene glycol, dimethyl sulfoxide and dimethylformamide. In some embodiments, the dispersant is selected from: block polymer P127, block polymer P123, polyethylene oxide, polyethylene glycol, disodium lauryl sulfosuccinate, disodium cocomonoethanolamide sulfosuccinate, monolauryl phosphate, potassium monolauryl phosphate, lauryl alcohol ether phosphate, potassium lauryl alcohol ether phosphate, ammonium fatty alcohol polyoxyethylene ether sulfate, cocomonoethanolamide, and at least one of cocoethyleneglycolamide. The solvents and the dispersing agents adopted in the embodiment of the invention have better dispersing effect on the metal monoatomic atoms and the substrate material, can effectively prevent the metal monoatomic atoms from agglomerating and deactivating in the solution, and is beneficial to the subsequent hydrothermal reaction of the metal monoatomic mixed solution and the substrate material; in addition, the solvents and the dispersing agents adopted in the embodiment of the invention are colorless and transparent, have small scattering on laser beams, and cannot influence the excitation treatment of the laser on metal materials in the mixed solution.
In some embodiments, as shown in fig. 1, a metal is placed in a mixed solution of a solvent and a dispersion liquid, an inert gas is introduced into the mixed solution through a gas inlet, the gas in the solution is removed and then removed from a gas outlet, and then the metal is subjected to laser treatment by using a laser so that a metal material enters the mixed solution in a monatomic form.
Specifically, in step S20, the metal monatomic mixed solution is mixed with a base material and then subjected to a hydrothermal reaction, so as to obtain a precursor loaded with a metal monatomic. According to the embodiment of the invention, the metal monoatomic mixed solution and the substrate material are mixed and then subjected to hydrothermal reaction, so that the metal monoatomic in the mixed solution is adsorbed onto the substrate material, and in the hydrothermal reaction process at a certain temperature, the metal monoatomic mixed solution and the substrate material form chemical combination, so that the interaction between the metal monoatomic mixed solution and the substrate material is enhanced, and the stability of the catalyst is improved. The substrate with the base material as the catalyst is used for anchoring metal monoatomic atoms, prevents the metal monoatomic atoms from agglomerating, improves the monoatomic stability and can enhance electron transmission.
In some embodiments, the step of hydrothermal reacting comprises: and mixing the metal monoatomic mixed solution with a substrate material, and reacting for 0.5-72 hours in a high-pressure reaction kettle at the temperature of 80-200 ℃. In the embodiment of the invention, the metal monatomic mixed solution and the substrate material mixture are subjected to hydrothermal reaction for 0.5 to 72 hours in a high-pressure reaction kettle at the temperature of 80 to 200 ℃, so that the metal monatomic and the substrate material are fully combined to form a precursor. If the temperature is too low or the reaction time is too short, the metal monoatomic atoms in the mixed solution are insufficiently combined with the substrate material, the content of the metal monoatomic atoms adsorbed on the substrate material is too low, and the catalytic effect of the subsequently prepared metal monoatomic catalyst is reduced.
In some embodiments, the volume ratio of the metal monoatomic mixed solution to the base material is (1.5 to 20): 1, the volume ratio is favorable for the hydrothermal reaction after the metal monoatomic mixed solution is mixed with the substrate material, so that the metal monoatomic mixed solution is fully combined with the substrate material. If the ratio of the metal monoatomic solution is too low or too high, the adsorption and combination between the metal monoatomic solution and the substrate material are not favorable.
In some embodiments, the substrate material is selected from: at least one of carbon material, carbide, sulfide, nitride and oxide. In some embodiments, the carbon material is selected from the group consisting of: at least one of active carbon, a metal organic framework material ZIF-8, a metal organic framework material ZIF-67, a carbon nano tube, graphite and graphene. In some embodiments, the carbide is selected from: at least one of tungsten carbide, titanium carbide, iron carbide and molybdenum carbide. In some embodiments, the oxide is selected from: at least one of aluminum oxide, silicon oxide, titanium oxide, vanadium oxide, manganese oxide, cobalt oxide, nickel oxide, iron oxide, copper oxide, zinc oxide, niobium oxide, molybdenum oxide, ruthenium oxide, iridium oxide, silver oxide, cadmium oxide, lanthanum oxide, cerium oxide, and samarium oxide. In some embodiments, the sulfide is selected from: at least one of iron sulfide, vanadium sulfide, nickel sulfide, cobalt sulfide, cadmium sulfide, niobium sulfide and zinc sulfide. In some embodiments, the nitride is selected from: at least one of titanium nitride, vanadium nitride, silicon nitride and boron nitride. The carbon material, carbide, sulfide, nitride, oxide, and other substrate materials used in the above embodiments of the present invention have non-metallic carbon, nitrogen, and oxygen as outer layers, and these carbon, nitrogen, and oxygen atoms and metal monoatomic atoms can form chemical bond, so that the metal monoatomic atoms are anchored on the surface of the substrate material to form chemical bonds of metal monoatomic atoms-O, metal monoatomic atoms-C, and metal monoatomic atoms-N, thereby improving the bonding stability of the metal monoatomic atoms and the substrate material, effectively preventing monoatomic agglomeration, and ensuring the catalytic performance of the metal monoatomic catalyst.
Specifically, in step S30, the precursor and the nitrogen-containing compound are mixed and then sintered in the second protective gas atmosphere, so as to obtain the nitrogen-doped metal monatomic catalyst. According to the embodiment of the invention, the precursor and the nitrogen-containing compound are mixed and then sintered, wherein the nitrogen-containing compound is thermally decomposed in the sintering process, and nitrogen atoms can be doped into the substrate material to form chemical bonds with metal single atoms in the sintering process, so that the bonding stability of the metal single atoms and the substrate material can be improved, the conductivity and the ionic conductivity of the catalyst can be improved, and the catalytic performance of the catalyst can be effectively improved. The second protective gas can ensure that the metal elements keep activity in the sintering process and avoid being damaged by oxidation.
In some embodiments, the step of sintering comprises: after the precursor and the nitrogen-containing compound are mixed, the mixture is heated to 400-1200 ℃ at the heating rate of 1-50 ℃/min and reacts for 0.5-72 hours. In the embodiment of the invention, after the precursor and the nitrogen-containing compound are mixed, the mixture is heated to 400-1200 ℃ at the heating rate of 1-50 ℃/min and reacts for 0.5-72 hours, if the heating rate is too high, the reaction speed is too high, and the nitrogen-containing compound cannot react with the precursor; if the sintering temperature is too low, enough energy is not available to enable the nitride to react with the precursor after being heated and decomposed, and nitrogen atoms cannot be doped into the substrate material to form combination with metal single atoms; if the temperature is too high, the nitrogen is decomposed and volatilized too fast, and does not flow into the precursor after being doped with nitrogen atoms; if the reaction time is too short or too long, the doping amount of nitrogen in the precursor is not favorable, so that the catalytic effect and the stability of the prepared metal monatomic catalyst are influenced.
In some embodiments, the mass ratio of the precursor to the nitrogen-containing compound is 1: (0.001-0.3). According to the embodiment of the invention, the mass ratio of the precursor to the nitrogen-containing compound is 1: (0.001-0.3), and sintering, wherein the doping proportion of nitrogen elements in the precursor is fully ensured by the material components in the proportion, so that the metal monatomic catalyst prepared by sintering has excellent catalytic effect and stability. If the mass ratio of the content of the nitrogen-containing compound is too low, the content of nitrogen element doped in the catalyst is too low, which is not beneficial to improving the combination stability of metal single atoms in the catalyst and is also not beneficial to improving the catalytic effect of the catalyst.
In some embodiments, the nitrogen-containing compound is selected from: at least one of melamine, cyanuric acid, triethylamine, ammonium borate, ammonium bicarbonate, ammonium sulfate, ammonium chloride and ammonium nitrate, wherein the nitrogen-containing compounds can be heated and decomposed to generate ammonia gas and carbon nitrogen compounds in the high-temperature sintering process, so that nitrogen atoms are doped into the substrate material to form chemical combination with metal single atoms, and the conductivity and the stability of the catalyst are improved.
In some embodiments, the second shielding gas is selected from: the catalyst comprises at least one of nitrogen, argon, helium, hydrogen, ammonia and methane, wherein inert gases such as nitrogen, argon and helium can prevent metal monatomic from being oxidized, and reducing gases such as hydrogen, ammonia and methane can reduce partial metal oxides, nitrides and carbides, so that the content of metal monatomic, nitrogen and carbon elements in the catalyst is ensured.
In some embodiments, the nitrogen-doped metal monatomic catalyst has a metal monatomic content of 0.2% to 7%. The content of metal single atoms in the nitrogen-doped metal single atom catalyst prepared by the embodiment of the invention is 0.2-7%, and the catalytic activity of the catalyst is effectively ensured.
Correspondingly, the embodiment of the invention also provides a metal monatomic catalyst, and the metal monatomic catalyst is prepared by the preparation method of the metal monatomic catalyst.
The metal monatomic catalyst provided by the embodiment of the invention is prepared by the method of the embodiment, the metal monatomic is well combined with the substrate material, the content of the metal monatomic in the catalyst is 0.2% -7%, the metal monatomic activity is high, and the catalytic effect is good; and the nitrogen element is doped in the catalyst, so that the combination stability of the metal monoatomic atoms and the substrate material can be improved, the conductivity of the catalyst can be improved, and the catalytic effect is further improved.
In order to make the details and operation of the above-mentioned embodiments of the present invention clearly understood by those skilled in the art and to make the performance of the metal monatomic catalyst and the method for preparing the same according to the embodiments of the present invention remarkably improved, the above-mentioned technical solutions are exemplified by a plurality of examples below.
Example 1
A metal monoatomic catalyst includes the following preparation steps:
1) The cobalt metal block was placed in a 30ml ethanol solution containing 0.1wt% of block polymer P123.
2) Excess argon was passed through the solution.
3) And irradiating the surface of the metal cobalt by a visible laser with the laser power of 30w to enable the cobalt atoms to enter the solution in a form, wherein the irradiation time is 0.2h.
4) And ultrasonically mixing the metal monoatomic dispersion solution with ZIF-8, and reacting for 5 hours in a high-pressure reaction kettle at the temperature of 80 ℃. Centrifugally separating to obtain a cobalt monoatomic-loaded ZIF-8 precursor;
5) The precursor material is mixed with 20wt% of ammonium chloride, and then is calcined for 2 hours at 400 ℃ in an argon atmosphere, so that the metal monatomic catalyst Co-N-C can be finally obtained, the mass percentage of cobalt atoms is shown in table 1, and the obtained catalyst is applied to 0.1mol/L HClO 4 Solution, oxygen reduction performance is tested.
Example 2
A metal monoatomic catalyst includes the following preparation steps:
1) Cobalt metal powder was placed in 50ml of an ethanol solution containing 5% by weight of P127.
2) The solution was purged with excess nitrogen.
3) Irradiating the surface of the metal cobalt by a visible laser with the laser power of 100w to ensure that the cobalt atom enters the solution, wherein the irradiation time is 0.5h.
4) The metal monoatomic solution and the active carbon are stirred and mixed, and then the mixture reacts for 6 hours in a high-pressure reaction kettle at the temperature of 120 ℃. Centrifugally separating to obtain an activated carbon precursor loaded with cobalt monoatomic atoms;
5) The precursor material is mixed with 0.1wt% of ammonium nitrate, and then is calcined for 5 hours at 1200 ℃ in an argon atmosphere, so that the metal single-atom catalyst Co-N-C can be finally obtained, the mass percentage of cobalt atoms is shown in table 1, and the obtained catalyst is applied to a 0.1mol/L KOH solution to test the oxygen reduction performance.
Example 3
A metal monatomic catalyst comprising the following preparation steps:
1) The iron metal block was placed in a solution of 100ml of 10wt% coco glycol amide in methylene chloride.
2) Excess argon was passed through the solution.
3) Irradiating the surface of the metal cobalt by a visible laser with the laser power of 500w to enable the iron atoms to enter the solution in a form, wherein the irradiation time is 0.2h.
4) And stirring and mixing the metal monoatomic dispersion solution and the graphene oxide, and reacting for 72 hours in a high-pressure reaction kettle at 200 ℃. Carrying out centrifugal separation to obtain an active graphene oxide precursor loaded with a cobalt monoatomic atom;
5) The precursor material is mixed with 30wt% of melamine, and then calcined for 15h at 900 ℃ in the mixed atmosphere of argon and hydrogen, finally the metal monatomic catalyst Fe-N-C can be obtained, the mass percentage of iron atoms is shown in table 1, and the obtained catalyst is applied to 0.1mol/L KHCO 3 And (4) testing the reduction performance of carbon dioxide.
Example 4
A metal monatomic catalyst comprising the following preparation steps:
1) The platinum metal sheet was placed in a container containing 120ml of an aqueous solution containing 0.2wt% of lauryl alcohol ether phosphate.
2) Excess argon was passed through the solution.
3) Irradiating the surface of the metal platinum by a visible laser with the laser power of 1000w to ensure that the platinum atoms enter the solution in a form, wherein the irradiation time is 5h.
4) The metal monoatomic solution is mixed with graphite and reacted in a high pressure reactor at 200 deg.c for 5 hr. Centrifugally separating to obtain a carbon nano tube precursor loaded with cobalt monoatomic atoms;
5) Calcining the precursor material and 20.6wt% of triethylamine at 1000 ℃ for 72H in argon atmosphere to finally obtain the metal single-atom catalyst Pt-N-C, wherein the mass percentage of platinum atoms is shown in Table 1, and the obtained catalyst is applied to 0.5mol/L H 2 SO 4 Solution, test hydrogen evolution catalytic performance.
Example 5
A metal monoatomic catalyst includes the following preparation steps:
1) The gold powder was placed in 80ml of a 10wt% potassium monododecyl phosphate in ethylene glycol.
2) Excess argon was passed through the solution.
3) Irradiating the surface of the metal platinum by a visible laser with the laser power of 800w to enable platinum atoms to enter the solution in a form, wherein the passing irradiation time is 3h.
4) The metal monoatomic solution is mixed with the alumina powder and reacted for 10 hours at 120 ℃ in a high-pressure reaction kettle. Centrifugally separating to obtain a carbon nano tube precursor loaded with cobalt monoatomic atoms;
5) The precursor material and 12.7wt% of ammonium chloride are calcined for 52 hours at 600 ℃ in an ammonia atmosphere, and finally the metal monoatomic catalyst Au-N-C can be obtained, wherein the mass percentage of gold atoms is shown in Table 1, and the obtained catalyst is applied to catalytic hydrogenation reaction of acetylene at 120 ℃.
Example 6
A metal monoatomic catalyst includes the following preparation steps:
1) The cobalt powder was placed in a container containing 80ml of a 10wt% solution of potassium monododecyl phosphate in ethylene glycol.
2) Excess argon was passed through the solution.
3) Irradiating the surface of the metal platinum by a visible laser with the laser power of 120w to ensure that the platinum atoms enter the solution in a form, wherein the irradiation time is 0.8h.
4) The metal monoatomic dispersion solution is mixed with cobaltosic oxide powder and reacts for 6 hours in a high-pressure reaction kettle at the temperature of 150 ℃. Carrying out centrifugal separation to obtain a cobaltosic oxide precursor loaded with cobalt monoatomic atoms;
5) The precursor material and 7.9wt% of cyanuric acid are calcined for 0.5h at 400 ℃ in the methane atmosphere, and finally the metal monatomic catalytic Co-Co can be obtained 3 O 4 The mass percentage of cobalt atoms is shown in Table 1, and the obtained catalyst is applied to 0.1mol/L KOH solution to test the catalytic performance of the total hydrolysis.
Example 7
A metal monoatomic catalyst includes the following preparation steps:
1) Manganese metal was placed in 60ml of isopropanol solution containing 3.8wt% disodium cocomonoethanolamide sulfosuccinate.
2) Excess argon was passed through the solution.
3) Irradiating the surface of the metal platinum by a visible laser with the laser power of 80w to ensure that the platinum atoms enter the solution in a form, wherein the irradiation time is 1.9h.
4) The solution with the metal monoatomic dispersion is mixed with silicon nitride and reacts for 18 hours in a high-pressure reaction kettle at the temperature of 130 ℃. Centrifugally separating to obtain a silicon nitride precursor loaded with manganese monoatomic atoms;
5) The precursor material and 8.0wt% of ammonium sulfate are calcined for 36h at 900 ℃ in hydrogen atmosphere, and finally the metal monatomic catalytic Mn-Si can be obtained 3 N 4 The mass percentage of manganese atoms is shown in table 1, and the obtained catalyst is applied to 0.1mol/L Na 2 SO 4 、0.1mol NaSO 3 And 0.01mol of Na 2 And S solution, and testing the photoelectric catalytic performance.
Example 8
A metal monatomic catalyst comprising the following preparation steps:
1) The metal was placed in 60ml of a dimethyl sulfoxide solution containing 6.9% by weight of polyethylene oxide.
2) The solution was purged with excess nitrogen.
3) Irradiating the surface of the metal platinum by a visible laser with laser power of 890w to ensure that the platinum atoms enter the solution in a form, wherein the irradiation time is 3.6h.
4) The metal monoatomic dispersion solution is mixed with titanium carbide and reacts for 10 hours in a high-pressure reaction kettle at 180 ℃. Carrying out centrifugal separation to obtain an iridium-loaded monoatomic titanium carbide precursor;
5) Calcining the precursor material and 25.6wt% of ammonium bicarbonate for 54h at 800 ℃ under the argon atmosphere to finally obtain the metal monatomic catalytic Ir-Ti 3 C 2 The mass percentage of iridium atoms is shown in Table 1, and the obtained catalyst is applied to 0.1mol/L KOH solution to test the oxygen precipitation catalytic performance.
Example 9
A metal monatomic catalyst comprising the following preparation steps:
1) The metal ruthenium was placed in 120ml of dimethylformamide containing 18% by weight of ammonium fatty alcohol polyoxyethylene ether sulfate.
2) The solution was purged with excess nitrogen.
3) Irradiating the surface of the metal platinum by a visible laser with the laser power of 750w to ensure that the platinum atoms enter the solution in a form, wherein the irradiation time is 2.5h.
4) The solution with the metal monoatomic dispersion is mixed with cadmium sulfide and reacts for 1 hour in a high-pressure reaction kettle at the temperature of 80 ℃. Centrifugally separating to obtain a ruthenium monoatomic loaded cadmium sulfide precursor;
5) Calcining the precursor material and 13.9wt% of melamine at 550 ℃ for 17 hours in argon atmosphere to finally obtain the metal monatomic catalytic Ru-CdS, wherein the mass percentage of the ruthenium atoms is shown in Table 1, and the obtained catalyst is applied to 0.5mol/L H 2 SO 4 And (4) testing the oxygen evolution catalytic performance of the solution.
Further, in order to verify the advancement of the metal monatomic catalyst prepared in the examples of the present invention, the examples of the present invention were subjected to a performance test.
Test example 1
The present invention measured the content of metal monoatomic atoms in the metal monoatomic catalysts prepared in examples 1 to 9, and the test results are shown in the following table 1:
TABLE 1
Test example 2
The invention adopts a high-angle annular dark field scanning transmission electron microscope to observe the metal monoatomic catalysts prepared in the embodiments 1-4, the transmission electron microscope pictures are respectively shown as the accompanying drawings 2-5, and the metal monoatomic catalysts prepared in the embodiments are uniformly distributed in the catalysts.
Test example 3
Further, the performances of the metal monatomic catalysts prepared in examples 1 to 9 are respectively tested, and the specific test results are respectively shown in table 1 above, so that the metal monatomic catalyst prepared in the examples of the present invention has good stability and catalytic performance.
The above description is intended to be illustrative of the preferred embodiment of the present invention and should not be taken as limiting the invention, but rather, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (9)
1. A preparation method of a metal monatomic catalyst is characterized by comprising the following steps:
performing laser treatment on a mixed solution containing a metal material and a dispersing agent in a first protective gas atmosphere to obtain a metal monoatomic mixed solution; wherein the mixed solution comprises a metal material, a solvent and a dispersant; the mass percentage of the metal monoatomic atoms in the metal monoatomic mixed solution is 0.1% -5%;
mixing the metal monoatomic mixed solution with a substrate material, and then carrying out hydrothermal reaction to obtain a precursor loaded with metal monoatomic;
mixing the precursor with a nitrogen-containing compound in a second protective gas atmosphere, and then sintering to obtain a nitrogen-doped metal monatomic catalyst;
wherein the metal material is selected from: at least one metal simple substance of iron, cobalt, nickel, copper, manganese, platinum, palladium, gold, silver, ruthenium, iridium and tungsten, or an alloy formed by at least two metals of iron, cobalt, nickel, copper, manganese, platinum, palladium, gold, silver, ruthenium, iridium and tungsten;
the dispersant is selected from: at least one of block polymer P127, block polymer P123, polyethylene oxide, polyethylene glycol, disodium lauryl sulfosuccinate, disodium cocomonoethanolamide sulfosuccinate, monolauryl phosphate, potassium monolauryl phosphate, lauryl alcohol ether phosphate, potassium lauryl alcohol ether phosphate, ammonium fatty alcohol polyoxyethylene ether sulfate, coco monoethanolamide, and coco ethylene glycol amide;
the hydrothermal reaction comprises the following steps: and mixing the metal monoatomic mixed solution with a substrate material, and reacting in a high-pressure reaction kettle at the temperature of 80-200 ℃ for 0.5-72 hours.
2. The method of preparing a metal monatomic catalyst according to claim 1, wherein the laser treatment step comprises: irradiating the metal material in the mixed solution containing the metal material with a laser with power of 30W to 1000W for 0.01 to 5 hours.
3. The method for producing a metal monoatomic catalyst according to claim 2, wherein a content of the dispersant is 0.01 to 10% based on 100% by mass of the mixed solution containing the metal material; and/or the presence of a gas in the gas,
the laser is selected from the following types: at least one of far infrared laser, mid-infrared laser, near-infrared laser, visible laser, and near-ultraviolet laser.
4. The method for preparing a metal monatomic catalyst according to claim 3, wherein the solvent in the mixed solution is selected from the group consisting of: at least one of water, methanol, ethanol, acetone, dichloromethane, isopropanol, ethylene glycol, dimethyl sulfoxide and dimethylformamide.
5. The method for producing a metal monoatomic catalyst according to any one of claims 1 to 4, wherein a volume ratio of the metal monoatomic solution to the base material is (1.5 to 20): 1; and/or the presence of a gas in the atmosphere,
the substrate material is selected from: the material comprises at least one of a metal organic framework material ZIF-8, a metal organic framework material ZIF-67, a carbon material, a carbide, a sulfide, a nitride and an oxide.
6. The method of preparing a metal monatomic catalyst according to claim 5, wherein the carbon material is selected from the group consisting of: at least one of activated carbon, carbon nanotubes, graphite and graphene; and/or the presence of a gas in the gas,
the carbide is selected from: at least one of tungsten carbide, titanium carbide, iron carbide and molybdenum carbide; and/or the presence of a gas in the atmosphere,
the oxide is selected from: at least one of aluminum oxide, silicon oxide, titanium oxide, vanadium oxide, manganese oxide, cobalt oxide, nickel oxide, iron oxide, copper oxide, zinc oxide, niobium oxide, molybdenum oxide, ruthenium oxide, iridium oxide, silver oxide, cadmium oxide, lanthanum oxide, cerium oxide, and samarium oxide; and/or the presence of a gas in the gas,
the sulfide is selected from: at least one of iron sulfide, vanadium sulfide, nickel sulfide, cobalt sulfide, cadmium sulfide, niobium sulfide and zinc sulfide; and/or the presence of a gas in the gas,
the nitride is selected from: at least one of titanium nitride, vanadium nitride, silicon nitride and boron nitride.
7. The method for preparing the metal monatomic catalyst according to any one of claims 1 to 4 or 6, wherein the sintering treatment comprises: mixing the precursor with a nitrogen-containing compound, heating to 400-1200 ℃ at a heating rate of 1-50 ℃/min, and reacting for 0.5-72 hours; and/or the presence of a gas in the gas,
the mass ratio of the precursor to the nitrogen-containing compound is 1: (0.001 to 0.3); and/or the presence of a gas in the atmosphere,
the nitrogen-containing compound is selected from: at least one of melamine, cyanuric acid, triethylamine, ammonium borate, ammonium bicarbonate, ammonium sulfate, ammonium chloride and ammonium nitrate.
8. The method of preparing a metal monatomic catalyst according to claim 7, wherein the first protective gas is selected from the group consisting of: at least one of nitrogen, argon, helium; and/or the presence of a gas in the atmosphere,
the second shielding gas is selected from: at least one of nitrogen, argon, helium, hydrogen, ammonia, and methane.
9. The method for preparing the metal monatomic catalyst according to any one of claims 1 to 4, 6 or 8, wherein the content of the metal monatomic in the nitrogen-doped metal monatomic catalyst is 0.2% to 7%.
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| CN108636437B (en) * | 2018-05-09 | 2021-03-26 | 天津理工大学 | Preparation method of nitrogen-doped carbon-supported metal monatomic catalyst |
| CN110064410A (en) * | 2019-05-10 | 2019-07-30 | 深圳大学 | A method of it is extremely easy to prepare the monatomic catalyst of noble metal |
| CN110449176B (en) * | 2019-08-16 | 2021-01-29 | 江南大学 | Preparation method and application of non-noble metal monatomic catalyst |
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