CN111426735A - Preparation and application of gold-cobalt @ nitrogen doped carbon nanotube hollow polyhedron - Google Patents
Preparation and application of gold-cobalt @ nitrogen doped carbon nanotube hollow polyhedron Download PDFInfo
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- CN111426735A CN111426735A CN202010403675.6A CN202010403675A CN111426735A CN 111426735 A CN111426735 A CN 111426735A CN 202010403675 A CN202010403675 A CN 202010403675A CN 111426735 A CN111426735 A CN 111426735A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 33
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 33
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 33
- REFJWTPEDVJJIY-UHFFFAOYSA-N Quercetin Chemical compound C=1C(O)=CC(O)=C(C(C=2O)=O)C=1OC=2C1=CC=C(O)C(O)=C1 REFJWTPEDVJJIY-UHFFFAOYSA-N 0.000 claims abstract description 85
- 229910017392 Au—Co Inorganic materials 0.000 claims abstract description 60
- ZVOLCUVKHLEPEV-UHFFFAOYSA-N Quercetagetin Natural products C1=C(O)C(O)=CC=C1C1=C(O)C(=O)C2=C(O)C(O)=C(O)C=C2O1 ZVOLCUVKHLEPEV-UHFFFAOYSA-N 0.000 claims abstract description 42
- HWTZYBCRDDUBJY-UHFFFAOYSA-N Rhynchosin Natural products C1=C(O)C(O)=CC=C1C1=C(O)C(=O)C2=CC(O)=C(O)C=C2O1 HWTZYBCRDDUBJY-UHFFFAOYSA-N 0.000 claims abstract description 42
- MWDZOUNAPSSOEL-UHFFFAOYSA-N kaempferol Natural products OC1=C(C(=O)c2cc(O)cc(O)c2O1)c3ccc(O)cc3 MWDZOUNAPSSOEL-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229960001285 quercetin Drugs 0.000 claims abstract description 42
- 235000005875 quercetin Nutrition 0.000 claims abstract description 42
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims abstract description 31
- 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 abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 26
- 239000010931 gold Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 238000001514 detection method Methods 0.000 claims abstract description 13
- 239000002105 nanoparticle Substances 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 8
- 238000002791 soaking Methods 0.000 claims abstract description 8
- 229910052737 gold Inorganic materials 0.000 claims abstract description 7
- 230000001681 protective effect Effects 0.000 claims abstract description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000011068 loading method Methods 0.000 claims abstract description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 5
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 53
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- 238000003756 stirring Methods 0.000 claims description 20
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 150000001868 cobalt Chemical class 0.000 claims description 6
- 150000003751 zinc Chemical class 0.000 claims description 6
- 238000001903 differential pulse voltammetry Methods 0.000 claims description 5
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 5
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000005259 measurement Methods 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 239000011148 porous material Substances 0.000 description 23
- 238000007254 oxidation reaction Methods 0.000 description 16
- 230000003647 oxidation Effects 0.000 description 15
- 238000006722 reduction reaction Methods 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 11
- 238000002484 cyclic voltammetry Methods 0.000 description 9
- 238000001069 Raman spectroscopy Methods 0.000 description 8
- 230000004044 response Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
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- 229910021607 Silver chloride Inorganic materials 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- WOAHJDHKFWSLKE-UHFFFAOYSA-N 1,2-benzoquinone Chemical compound O=C1C=CC=CC1=O WOAHJDHKFWSLKE-UHFFFAOYSA-N 0.000 description 5
- 241000234282 Allium Species 0.000 description 5
- 235000002732 Allium cepa var. cepa Nutrition 0.000 description 5
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000001103 potassium chloride Substances 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
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- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 230000027756 respiratory electron transport chain Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000001237 Raman spectrum Methods 0.000 description 3
- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
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- 239000000047 product Substances 0.000 description 3
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- WXTMDXOMEHJXQO-UHFFFAOYSA-N 2,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC=C1O WXTMDXOMEHJXQO-UHFFFAOYSA-N 0.000 description 2
- ACZGCWSMSTYWDQ-UHFFFAOYSA-N 3h-1-benzofuran-2-one Chemical class C1=CC=C2OC(=O)CC2=C1 ACZGCWSMSTYWDQ-UHFFFAOYSA-N 0.000 description 2
- 229910020676 Co—N Inorganic materials 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 2
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- 229940074391 gallic acid Drugs 0.000 description 2
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- RJAIDLWVKKIEJQ-DKWTVANSSA-N (2r)-2-amino-3-sulfanylpropanoic acid;gold Chemical compound [Au].SC[C@H](N)C(O)=O RJAIDLWVKKIEJQ-DKWTVANSSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 1
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- 241000218628 Ginkgo Species 0.000 description 1
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- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
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- 229960003178 choline chloride Drugs 0.000 description 1
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
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- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- JBFYUZGYRGXSFL-UHFFFAOYSA-N imidazolide Chemical compound C1=C[N-]C=N1 JBFYUZGYRGXSFL-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
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-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Abstract
The invention discloses a preparation method of a gold-cobalt @ nitrogen doped carbon nanotube hollow polyhedron, which comprises the following steps: (1) preparation of ZIF-8@ ZIF-67: taking ZIF-8 as an inner core, and epitaxially growing ZIF-67 on the ZIF-8 to obtain ZIF-8@ ZIF-67; (2) preparation of Co @ NCNHP: calcining ZIF-8@ ZIF-67 under protective gas, and soaking the calcined material with acid to remove surface metal oxide to obtain Co @ NCNHP; (3) preparation of Au-Co @ NCNHP: and loading the gold nanoparticles on the Co @ NCNHP under ice bath to obtain Au-Co @ NCNHP. The Au-Co @ NCNHP prepared by the method is used for constructing the electrochemical sensor of the quercetin, and has a wider detection range and a lower detection limit.
Description
Technical Field
The invention relates to the technical field of electrochemical sensors, in particular to preparation and application of a gold-cobalt @ nitrogen doped carbon nanotube hollow polyhedron.
Background
Metal ions (e.g. Zn)2+、Co2+) And an organic ligand (imidazole) can construct a Zeolite Imidazolate Framework (ZIFs) with a three-dimensional porous structure through coordination bonds. ZIFs have the advantages of high porosity and surface area, adjustable pore size, high chemical stability and thermal stability, and the like, and are widely applied to the fields of gas storage, separation, catalysis and the like. Among them, ZIF-8 containing zinc and ZIF-67 containing cobalt are two typical ZIFs materials except for the difference in metal ion (Zn)2+Or Co2+) In addition, both have the same topology, similar unit cell parameters and the same organic ligands, and both have rich carbon and nitrogen contents and high metal ion ratios. The ZIF @ ZIF material with the core-shell structure prepared from the material has relatively low preparation cost and good performance.
However, ZIF @ ZIF materials have poor conductivity and small electrochemical response, which in turn limits their application in electrochemical detection.
Therefore, the problem to be solved by those skilled in the art is how to provide a material suitable for electrochemical detection by using the ZIF @ ZIF material.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a gold-cobalt @ nitrogen doped carbon nanotube hollow polyhedron and application thereof in electrochemical detection.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the gold-cobalt @ nitrogen doped carbon nanotube hollow polyhedron comprises the following steps:
(1) preparation of ZIF-8@ ZIF-67
Taking ZIF-8 as an inner core, and epitaxially growing ZIF-67 on the ZIF-8 to obtain ZIF-8@ ZIF-67;
(2) preparation of Co @ NCNHP
Calcining ZIF-8@ ZIF-67 under protective gas, and soaking the calcined material with acid to remove surface metal oxide to obtain Co @ NCNHP;
(3) preparation of Au-Co @ NCNHP
And loading the gold nanoparticles on the Co @ NCNHP under ice bath to obtain Au-Co @ NCNHP.
According to the invention, ZIF-8@ ZIF-67 with a core-shell structure is calcined, a nitrogen-doped carbon nanotube hollow polyhedron (NCNHP) derived from high-temperature carbonization of the ZIF-67 serves as a hollow framework of a nanostructure, a zinc element in the ZIF-8 reacts to form a Zn simple substance and evaporates along with a protective gas, and carbon forms a large number of carbon nanotubes, so that the Co-loaded nitrogen-doped carbon nanotube hollow polyhedron (Co @ NCNHP) is obtained. Further, removing metal oxide on the surface of the material by acid soaking, and then loading the gold nanoparticles on Co @ NCNHP by boric acid to prepare the Au and Co bimetal loaded nitrogen-doped carbon nanotube hollow polyhedron (Au-Co @ NCNHP) with the core-shell structure. The preparation method is simple, and the obtained material has the advantages of uniform distribution of all elements, good conductivity and strong electrochemical response.
Preferably, step (1) is specifically as follows:
1) preparation of ZIF-8
Respectively dissolving soluble zinc salt and 2-methylimidazole in methanol to obtain a solution I and a solution II;
dropwise adding the solution II into the solution I, stirring, carrying out solid-liquid separation, washing and drying to obtain a ZIF-8 crystal;
2) preparation of ZIF-8@ ZIF-67
Dispersing ZIF-8 in methanol to obtain ZIF-8 suspension;
respectively dissolving soluble cobalt salt and 2-methylimidazole in methanol to obtain a solution III and a solution IV;
adding the solution III into the ZIF-8 suspension to obtain a mixed solution;
and adding the solution IV into the mixed solution, stirring, carrying out solid-liquid separation, washing and drying to obtain ZIF-8@ ZIF-67.
Further preferably, in step 1),
the soluble zinc salt comprises one or more of zinc nitrate, zinc sulfate or zinc acetate;
the mol ratio of the soluble zinc salt to the 2-methylimidazole is 1: 3-5;
dropwise adding the solution II into the solution I, stirring for 20-36h, centrifuging at 10000-;
in the step 2), the step (c) is carried out,
the soluble cobalt salt comprises one or more of cobalt nitrate, cobalt sulfate or cobalt acetate;
the dosage ratio of ZIF-8, soluble cobalt salt and 2-methylimidazole is 1 g: 0.03-0.05 mol: 0.1-0.25 mol;
after the solution four is added into the mixed solution, the stirring time is 20-36h, the centrifugation speed is 10000-13000r/min, and the drying temperature is 50-80 ℃.
Preferably, step (2) is specifically as follows:
calcining ZIF-8@ ZIF-67 at 915 ℃ and 950 ℃ for 3-5h by taking argon or nitrogen as protective gas;
cooling the material obtained by calcination in H2SO4Soaking in the solution, carrying out solid-liquid separation, and washing to obtain Co @ NCNHP;
the temperature rise rate before calcination does not exceed 5 ℃/min;
H2SO4the concentration of the solution is 0.7-0.9 mol/L, and the soaking time is 10-14 h.
Preferably, step (3) is specifically as follows:
dispersing Co @ NCNHP in an ethanol-water solution under ice bath, adding a chloroauric acid water solution, and stirring for 3-5 h; addition of NaBH was continued4Stirring the aqueous solution for reaction, wherein the stirring time is not more than 1h, and the stirring speed is not more than 2000 r/min; after the reaction, carrying out solid-liquid separation, washing and drying to obtain Au-Co @ NCNHP;
the volume fraction of ethanol in the ethanol-water solution is 25-50%;
co @ NCNHP, chloroauric acid in aqueous chloroauric acid solution, NaBH4NaBH in aqueous solution4The dosage ratio is 1 mg: 6-40 μ g: 1-8 mu mol.
Loading gold nanoparticles under ice bath (0-5 ℃), wherein the reaction speed can be controlled, so that a chloroauric acid solution is slowly diffused into a Co @ NCNHP pore channel, and the chloroauric acid can be slowly reduced when boric acid is also diffused into the pore channel, so that the gold nanoparticles are better embedded into the pore channel; the chloroauric acid aqueous solution is added and stirred for more than 3 hours, so that the chloroauric acid can be fully diffused into the pore channels of the material.
The gold-cobalt @ nitrogen doped carbon nanotube hollow polyhedron prepared by the preparation method is applied to the preparation of electrochemical sensors.
The gold-cobalt @ nitrogen doped carbon nanotube hollow polyhedron prepared by the preparation method is applied to the preparation of a chemically modified electrode.
The chemically modified electrode is characterized in that a gold-cobalt @ nitrogen doped carbon nanotube hollow polyhedron is modified on the surface of an electrode material, and the gold-cobalt @ nitrogen doped carbon nanotube hollow polyhedron is prepared by the preparation method.
Further, 1mg/m L suspension of the gold-cobalt @ nitrogen doped carbon nanotube hollow polyhedron is prepared, and the glassy carbon electrode is modified by adopting a direct dropping coating method.
The gold-cobalt @ nitrogen doped carbon nanotube hollow polyhedron prepared by the preparation method or the chemically modified electrode is applied to quercetin detection.
The chemical modified electrode is a working electrode, a quercetin determination standard curve is drawn by adopting a differential pulse voltammetry method, and the content of quercetin in a sample to be determined is determined by a standard addition method.
According to the technical scheme, a novel nano composite material (Au-Co @ NCNHP) is synthesized by adopting a pyrolysis-soaking-reduction reaction path for ZIF-8@ ZIF-67 with a core-shell structure, after the ZIF-8@ ZIF-67 is pyrolyzed, a large number of carbon nano tubes can be obtained on the surface of a hollow polyhedron, the carbon nano tubes play an active role in an electronic conduction process, Au is loaded on the Co @ NCNHP, the transmission of electrons is facilitated, the reaction process of the surface of an electrode is accelerated, GCE is used as a substrate electrode, the Au-Co @ NCNHP nano composite material is used for constructing an electrochemical sensor of quercetin, the detection range is 0.05-80.0 mu mol/L, and the detection limit is 0.023 mu mol/L, and the electrochemical sensor is successfully applied to quantitative analysis of quercetin in ginkgo biloba leaves and onions.
Drawings
FIG. 1 shows a preparation process of Au-Co @ NCNHP;
FIG. 2 shows SEM and TEM images of ZIF-8, ZIF-8@ ZIF-67;
wherein, A is an SEM picture of ZIF-8, B is an SEM picture of ZIF-8@ ZIF-67, C is a TEM picture of ZIF-8, and D is a TEM picture of ZIF-8@ ZIF-67;
FIG. 3 shows the morphological features of Au-Co @ NCNHP;
wherein A is SEM picture (the insert picture in A is magnified SEM picture), B is HAADF-STEM element scanning picture, C is TEM picture, and D-G is HRTEM picture;
FIG. 4 is a XRD spectrum for ZIF-8@ ZIF-67, Co @ NCNHP, Au-Co @ NCNHP;
FIG. 5 is a Raman spectrum of ZIF-8@ ZIF-67, Co @ NCNHP, Au-Co @ NCNHP;
FIG. 6 is a FT-IR spectrum showing ZIF-8@ ZIF-67, Co @ NCNHP, Au-Co @ NCNHP;
FIG. 7 is an XPS spectrum showing ZIF-8@ ZIF-67, Co @ NCNHP, Au-Co @ NCNHP;
wherein, A-F are respectively an all-element spectrogram, a C1s peak spectrogram, an N1s peak spectrogram, a Zn2p peak spectrogram, a Co2p peak spectrogram and an Au4F peak spectrogram;
FIG. 8 is a graph showing the results of pore size distribution characterization of ZIF-8@ ZIF-67, Co @ NCNHP, Au-Co @ NCNHP;
wherein A, B, C are respectively nitrogen isothermal adsorption-desorption curves of ZIF-8@ ZIF-67, Co @ NCNHP and Au-Co @ NCNHP; D. e, F are pore size distribution Plots (PSD) for ZIF-8@ ZIF-67, Co @ NCNHP, Au-Co @ NCNHP, respectively;
FIG. 9 shows EIS curves for different chemically modified electrodes;
wherein, a is GCE, b is ZIF-8@ ZIF-67/GCE, c is Co @ NCNHP/GCE, and d is Au-Co @ NCNHP/GCE;
FIG. 10 shows different chemically modified electrodes at 1 mmol/L [ Fe (CN)6]3-/4-And CV curve in 0.1 mol/L KCl mixture;
wherein, a is GCE, b is ZIF-8@ ZIF-67/GCE, c is Co @ NCNHP/GCE, and d is Au-Co @ NCNHP/GCE;
FIG. 11 shows CV curves of 100.0 μmol/L quercetin on various chemically modified electrodes;
wherein, a is GCE, b is ZIF-8@ ZIF-67/GCE, c is Co @ NCNHP/GCE, and d is Au-Co @ NCNHP/GCE;
FIG. 12 shows the effect of electrolyte pH on the quercetin reaction process on chemically modified electrodes;
wherein A is CV curve of quercetin on Au-Co @ NCNHP/GCE under different pH values (a → g: 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0); b is the relationship curve of E0' and Ipa with pH;
FIG. 13 is a graph showing the effect of sweep rate on the course of quercetin response on a chemically modified electrode;
wherein A, B is a CV curve on Au-Co @ NCNHP/GCE at different sweeping speeds; c is a relation curve of peak current and scanning speed to the power of one half; d is a relation curve of the peak potential and the logarithm of the scanning speed; (a → n: 0.01, 0.02, 0.03, 0.04, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9V/s);
FIG. 14 shows the results of a working curve measurement of quercetin;
wherein, A is DPV curve of quercetin with different concentrations, B is relation curve of oxidation peak current and quercetin (a → m: 0.05, 5.0, 10.0, 15.0, 20.0, 25.0, 30.0, 35.0, 40.0, 50.0, 60.0, 70.0, 80.0 μmol/L);
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the embodiment of the invention, an electrochemical workstation adopts CHI 832B (Shanghai Chenghua instruments, Inc., China), a Raman spectrum test adopts L ABRAM HR Evolution (JobinYvon, France), a high-speed centrifuge adopts H1850 (Hunan Xiang instruments laboratory Instrument development, China), and a non-contact ultrasonic cell crusher adopts SCIENTZ 08-III (Ningbo Xinzhi Biotechnology, Inc., China).
Chloroauric acid was purchased from Guangzhou state new chemical plant; sulfuric acid was purchased from west longa chemical ltd; sodium borate was purchased from Guangzhou reagent works; ginkgo biloba leaves were purchased from the Haikouqili pharmaceutical Co., Ltd; onion is purchased from the local vegetable in Hainan province; quercetin Standard, Co (NO)3)2·6H2O、Zn(NO3)2·6H2O, 2-methylimidazole (2-MIM) and methanol (MeOH) were purchased from Shanghai Allantin Biochemical Co., Ltd.
Example 1 preparation and study of gold-cobalt @ nitrogen doped carbon nanotube hollow polyhedron
As shown in fig. 1, the preparation of the gold-cobalt @ nitrogen-doped carbon nanotube hollow polyhedron Au-Co @ NCNHP comprises the following steps:
1. preparation of ZIF-8
Adding Zn (NO)3)2·6H2O (5.95g, 0.02mol) and 2-MIM (6.16g, 0.075mol) were dissolved in 150m L methanol (MeOH) respectively to give solution one and solution two;
and then dropwise adding the solution II into the solution I, stirring at room temperature for 24 hours, then centrifuging the white suspension at high speed (10000r/min) and washing the white suspension for several times by using MeOH, and drying in vacuum at the temperature of 60 ℃ to obtain the ZIF-8 crystal.
2. Preparation of ZIF-8@ ZIF-67
ZIF-8(0.5g) was dispersed in 100m L MeOH to form a white ZIF-8 suspension;
mixing Co (NO)3)2·6H2O (5.82g, 0.02mol) and 2-MIM (6.16g, 0.075mol) were dissolved in 100m L MeOH, respectively, to give solution three and solution four;
then slowly adding the solution III into the ZIF-8 suspension to obtain a mixed solution;
and slowly adding the solution IV into the mixed solution, mixing and stirring at room temperature for 24h, then centrifuging the light purple precipitate at high speed (10000r/min) and washing the precipitate for a plurality of times by using MeOH, and drying the precipitate in vacuum at the temperature of 60 ℃ to obtain ZIF-8@ ZIF-67.
3. Preparation of Co @ NCNHP
Putting ZIF-8@ ZIF-67 in a tube furnace, heating to 920 ℃ at a heating rate of 2 ℃/min for 3h by taking Ar as protective gas, and then cooling to room temperature at a cooling rate of 5 ℃/min;
the obtained black powder was mixed at 0.8 mol/L H2SO4The solution was soaked for 12h and the precipitate was spun at high speed (10000r/min) and washed several times with MeOH to give Co @ NCNHP.
4. Preparation of Au-Co @ NCNHP
Co @ NCNHP (40mg) was dispersed in a 4.0m L ethanol-water solution (V)Water (W)：VEtOH1:1), then 0.5m L1.3.1 mg/m L of aqueous chloroauric acid is added, the mixture is stirred for 4h, and then 2.4m L0.05.0.05 mol/L NaBH is added4Stirring the aqueous solution for reaction for 30min, wherein the stirring speed is not more than 2000 r/min; the preparation of Au-Co @ NCNHP was carried out in an ice bath (0-5 ℃ C.).
After the reaction, centrifugation was performed, washed several times with water and dried to obtain Au-Co @ NCNHP.
Further, the materials prepared in steps 1 to 4 were analyzed as follows:
1. the morphology of ZIF-8, ZIF-8@ ZIF-67 and Au-Co @ NCNHP is characterized as follows:
the ZIF-8 crystal is hexagonal, has a diameter of about 450nm, has a relatively smooth surface, and has no significant pores (fig. 2A, 2C).
Taking ZIF-8 as seed crystal, and epitaxially growing ZIF-67 to obtain ZIF-8@ ZIF-67 (FIG. 2B and 2D); the ZIF-8@ ZIF-67 crystal is dodecahedron in morphology, uniform in particle size and shape, smooth in surface, free of obvious pore channels and about 600nm in crystal diameter.
The morphology characteristics of Au-Co @ NCNHP are inspected through SEM and TEM, and the result shows that the material keeps the dodecahedron shape of a precursor ZIF-8@ ZIF-67, the diameter is about 600nm, the surface contains a large number of carbon nano tubes, and the surface is rough and porous (FIG. 3A); high angle annular dark field scanning transmission electron microscopy (HAADF-STEM) and X-ray energy spectroscopy analysis (EDS) (fig. 3B) results show that C, N, Co and the Au element are uniformly distributed throughout NCNHP; as can be seen from fig. 3C and 3D, the hollow dodecahedron is formed after calcination, and hollow carbon nanotubes with a diameter of 5.5nm are extended on the surface; FIGS. 3E-3G are TEM images of Au-Co @ NCNHP at different magnification with a metal particle size of about 15 nm.
2. X-ray diffraction (XRD) analysis was performed on ZIF-8@ ZIF-67, Co @ NCNHP, Au-Co @ NCNHP:
as shown in FIG. 4, the diffraction peaks of Co @ NCNHP at 25.9, 44.1, 51.4 and 75.9 correspond to the graphite type carbon (002) crystal face and the cobalt (111), (200), (220) crystal face [ PDF #15-0806], respectively.
Au-Co @ NCNHP has diffraction peaks at 38.2, 44.4, 64.6 and 78.8, corresponding to (111), (200), (220) and (311) crystal planes [ ICSD #76153] of Au, respectively; the diffraction peak of 44.4 is wide due to the superposition of diffraction peaks of Co (111) and Au (200) crystal planes.
3. Raman (Raman) spectroscopy was performed on ZIF-8@ ZIF-67, Co @ NCNHP, Au-Co @ NCNHP:
as shown in FIG. 5, 176cm in ZIF-8@ ZIF-67-1Is a characteristic peak of M-N (M represents Co or Zn), 465cm-1And 515cm-1Represents a characteristic peak of M-O-M, 677.3cm-1Represents the Raman vibration peak of the heterocycle in the imidazole.
1341cm in Co @ NCNHP-1The Raman characteristic peak of (A) is a D peak and corresponds to sp3The characteristic peak of hybridized carbon atoms is mainly the characteristic peak formed by the vibration of disordered carbon in the material; 1584cm-1The Raman characteristic peak of (A) is a G peak, mainly sp in graphite carbon2Characteristic peaks formed by vibration of hybridized carbon atoms forming a hexagonal lattice structure; i isD/IGThe value of (A) is 0.786.
The Raman characteristic peak of Au-Co @ NCNHP is the same as the characteristic peak of Co @ NCNHP in position, the intensity is increased, ID/IGThe value of (A) is 0.976. I isD/IGIs an index for measuring the number of structural defects in the carbon material, ID/IGAn increase in value indicates an increase in the degree of disorder of the material; au nanoparticles formed by reduction of chloroauric acid through boric acid are loaded on the carbon material, so that the defects of the carbon material are increased, the graphitization degree is reduced, part of skeleton carbon atoms are converted into impurity carbon atoms, and the impurity carbon atoms are increased. In addition, Au has the capability of enhancing Raman signals, the Raman characteristic peak intensity is increased, and further the Au is successfully loaded on Co @ NCNHP.
4. Fourier transform Infrared Spectroscopy (FT-IR) was used to compare the changes in ZIF-8@ ZIF-67, Co @ NCNHP, Au-Co @ NCNHP functional groups:
as shown in the figureShown as 6, in ZIF-8@ ZIF-67, 2929cm-1The infrared characteristic peak belongs to C-H stretching vibration, 1630cm-1The position belongs to the characteristic peak of O-H bending vibration, 1584cm-1The position is C-N telescopic vibration absorption peak, 1350--1Is a telescopic vibration characteristic peak of the whole pyridine ring convolution, 900-1350cm-1The absorption peak in the interval is caused by the in-plane bending vibration of pyridine ring, and is less than 800cm-1The absorption band of (a) is the characteristic peak of out-of-plane bending vibration of pyridine ring, 421cm-1Is the stretching vibration absorption peak of Zn-N and Co-N, which shows that Zn2+And Co2+Coordinating with 2-MIM to form ZIF-8@ ZIF-67.
Co @ NCNHP and Au-Co @ NCNHP at 421cm-1There is no diffraction peak, which shows that Zn-N and Co-N are broken after calcination; at 1200-700 cm-1A wider and weak absorption peak belongs to a C-C vibration characteristic peak; at 1680-1620 cm-1C is C vibration characteristic peak; indicating the formation of a carbon composite with a higher degree of graphitization. Au is loaded on Co @ NCNHP, no other obvious characteristic peak appears, and the spectrum is basically consistent with that of the Co @ NCNHP, and further shows that Au is loaded on the Co @ NCNHP in a nanoparticle form.
5. The compositions of ZIF-8@ ZIF-67, Co @ NCNHP and Au-Co @ NCNHP were characterized by X-ray photoelectron spectroscopy (XPS) techniques:
as can be seen from the full-element spectrogram (FIG. 7A), the Zn element disappears, the N element content is reduced, and the C element content is increased after the ZIF-8@ ZIF-67 is calcined; the diffraction peak of Au4f was observed in the range of 80eV to 100eV, indicating that Au was successfully supported on Co @ NCNHP.
FIG. 7B is an elemental analysis chart of C1s in the range of 280eV to 298eV, illustrating that three different forms of the carbon element exist for ZIF-8@ ZIF-67: sp2Hybrid graphitic carbon, i.e. C ═ C (284.6 ± 0.2eV), C — N (285.2 ± 0.2eV), C — O (285.8 ± 0.2 eV); c1s for Co @ NCNHP and Au-Co @ NCNHP also present C ═ O (288.1 ± 0.2 eV). The corresponding existing forms of the three nano-composite materials have different peak intensities, wherein ZIF-8@ ZIF-67 contains abundant C-N components (from an organic ligand 2-MIM); co @ NCNHP and Au-Co @ NCNHP have abundant C ═ C components, and since abundant graphitic carbon is formed after calcination, the results are consistent with Raman spectra。
As shown in FIG. 7C, N1s of ZIF-8@ ZIF-67 has both pyrrole nitrogen (400. + -. 0.2eV) and pyridine nitrogen (398.4. + -. 0.2eV) present therein, and is derived from 2-MIM; the presence of pyrrole nitrogen, pyridine nitrogen, oxynitride (402.8 + -0.2 eV), and graphitic nitrogen (401 + -0.2 eV) in Co @ NCNHP and Au-Co @ NCNHP indicates that some of the pyridine or pyrrole nitrogen components in 2-MIM are converted to nitroxide and graphitic nitrogen after high temperature carbonization.
As with the Zn2p spectrum in FIG. 7D, the two major peaks appearing at 1044eV and 1021eV are Zn2p1/2And Zn2p3/2Characteristic peak of (2).
In FIG. 7E, the diffraction peaks at 797.3eV and 780.3eV are Co2p1/2And Co2p3/2Characteristic peak of (2). The fitted spectra at 798.3eV and 781.0eV are Co2+A characteristic peak of (1), two peaks near the binding energies of 796.2eV and 779.6eV corresponding to Co3+Characteristic peaks, the minor peaks of 801.3eV, 785.8eV and 783.3eV being Co vibro-satellite peaks; co @ NCNHP and Au-Co @ NCNHP have no Co3+And Co2+The characteristic peaks and satellite peaks indicate that no metal oxide was formed during calcination.
FIG. 7F shows two characteristic peaks of Au4F, and two main peaks of 84.0eV and 87.7eV are Au4F7/2And Au4f5/2The results indicate that Au was successfully supported on Co @ NCNHP.
Characterization of pore size distribution for ZIF-8@ ZIF-67, Co @ NCNHP and Au-Co @ NCNHP:
ZIF-8@ ZIF-67 at lower relative pressures (P/P)00.02), the isotherm shows a significant and steep rise and then bends to form a plateau, the adsorption capacity does not change significantly with the increase of pressure, and no hysteresis loop exists, and the isotherm is a typical type I isotherm, which shows that the ZIF-8@ ZIF-67 only has micropores (FIG. 8A).
The PSD of ZIF-8@ ZIF-67 shows (FIG. 8D) that the pore sizes of micropores are mainly distributed at 0.6nm and 1.8nm, and the specific surface area and the pore volume are 1174m, respectively, as calculated by the BET-BJH method2G and 0.24cm3/g。
Co @ NCNHP and Au-Co @ NCNHP both belong to type IV isotherms (FIGS. 8B and 8C), and the adsorption curves show obvious large and steep rises under extremely low relative pressuresAt relatively moderate pressure (0.4P/P)00.9), the adsorption curve rises slowly, the relative pressure is in the range of 0.9-1.0, and an obvious hysteresis (the adsorption curve is inconsistent with the desorption curve) exists, which indicates that the material has mesopores; the hysteresis loop of Au-Co @ NCNHP is closed more slowly, which shows that more mesopores exist and the pore size distribution is wider.
The PSD of Co @ NCNHP shows (FIG. 8E) that the pore diameters of the micropores of the material are mostly distributed at 0.8nm, the pore diameter of the mesopore is 3.8nm, and the specific surface area and the pore volume are 236m respectively2G and 0.08cm3/g。
The PSD chart of Au-Co @ NCNHP shows (FIG. 8F) that the pore diameters of micropores are distributed at 0.7nm and 1.7nm, the pore diameters of mesopores are distributed at 3.8nm, and the specific surface area and the pore volume are 204m respectively2G and 0.09cm3The PSD is matched with the result of the nitrogen isothermal adsorption-desorption curve.
The above table and calculation results show that the pore size of the ZIF-8@ ZIF-67 derived carbon material is obviously increased, and the pore size is changed from a microporous carbon material to a micro-mesoporous carbon material.
EXAMPLE 2 preparation of chemically modified electrode and study of electrochemical Properties thereof
Respectively taking 1.0mg ZIF-8@ ZIF-67, Co @ NCNHP and Au-Co @ NCNHP to be dispersed in a 1.0m L aqueous solution by using an ultrasonic cell crusher to prepare a ZIF-8@ ZIF-67 suspension, a Co @ NCNHP suspension and an Au-Co @ NCNHP suspension of 1.0mg/m L, respectively transferring 8.0 mu L of the suspensions by using a liquid transfer gun to be dripped on the surface of a polished glassy carbon electrode GCE, and naturally airing to obtain chemically modified electrodes ZIF-8@ ZIF-67/GCE, Co @ NCNHP/GCE and Au-Co @ NCNHP/GCE.
The electrochemical properties of the chemically modified electrode are verified as follows:
1. at a rate of 10.0 mmol/L [ Fe (CN)6]3-/4-And 0.1 mol/L KCl mixed solution is used as an electrochemical test solution, different chemically modified electrodes are used as working electrodes (3 mm), an Ag/AgCl electrode (saturated KCl solution) is used as a reference electrode, a platinum wire electrode is used as a counter electrode, the electrochemical performances of the different chemically modified electrodes are represented by an alternating current impedance method (EIS), the semicircular diameter is fitted by a computer to obtain an impedance value (Rct), and the result is shown in figure 9.
GCE (a), ZIF-8@ ZIF-67/GCE (b), Co @ NCNHP/GCE (c) and Au-Co @ NCNHP/GCE (d) have Rct values of 455, 12900, 197 and 48.9, respectively.
Due to poor conductivity of ZIF-8@ ZIF-67, the Rct value of a chemically modified electrode is increased by 2 orders of magnitude compared with that of a bare electrode, and the existence of the material obviously prevents [ Fe (CN) ]6]3-/4-Electron transfer at the electrode surface.
The Co @ NCNHP formed after calcination has the advantages that the conductivity of the modified electrode surface is enhanced due to the existence of the Co simple substance and the high-conductivity nitrogen-doped porous carbon in the material, the electron transfer rate is accelerated, and the Rct value is obviously reduced.
After Au is loaded on Co @ NCNHP, the Au further enhances the conductivity of the composite nano material, the electron transfer rate of an electrode interface is effectively improved, and the Rct value is obviously reduced.
2. With [ Fe (CN) ]6]3-/4-For redox probe, different chemically modified electrodes were used as working electrodes (═ 3mm), Ag/AgCl electrodes (saturated KCl solution) as reference electrodes, platinum wire electrodes as counter electrodes, and the values of the different chemically modified electrodes were recorded at 1.0 mmol/L [ Fe (CN)6]3-/4-And Cyclic Voltammetry (CV) curves in a 0.1 mol/L KCl mixed solution (FIG. 10).
GCE (a) A symmetric pair of [ Fe (CN) ]appearing around 0.23V6]3-/4-Reduction oxidation peak (2/2').
ZIF-8@ ZIF-67/GCE showed a pair of asymmetric, weakly responsive redox peaks near 0.15V, [ Fe (CN)6]3-/4-The peak position shifts due to Zn2+And Co2+The presence of (a) causes an irreversible redox reaction; the electrochemical response is weak because of the poor conductivity of ZIF-8@ ZIF-67.
Co @ NCNHP/GCE (c) and Au-Co @ NCNHP/GCE (d) at about 0.52V a Co (IV) + e- 
Co (III) reduction peak (1/1'), appearing near 0.25V [ Fe (CN)6]3-/4-Reduced oxidation peak (2/2'), Co (III) + e appearing near-0.13V- 
The reduction peak (3/3') of Co (II) has the specific electrochemical parameters shown in Table 1.
TABLE 1 electrochemical parameters of different chemically modified electrodes
The results show that ZIF-8@ ZIF-67 has poor conductivity and small electrochemical response; the Co @ NCNHP has better electrochemical response, and probably because the surface of the hollow dodecahedron is attached with the carbon nano tube and the uniformly distributed cobalt simple substance, the conductivity of the material is enhanced, and a pore channel structure beneficial to small molecule adsorption is provided. After Au nanoparticles are loaded on Co @ NCNHP, the Au nanoparticles which are uniformly distributed further improve the electrochemical performance, so that the electrochemical response of the chemically modified electrode is obviously enhanced.
Example 3 electrochemical behavior study of Quercetin
1. The different chemically modified electrode prepared in example 2 was used as a working electrode (phi. 3mm), an Ag/AgCl electrode (saturated KCl solution) was used as a reference electrode, a platinum wire electrode was used as a counter electrode, and the pH of the solution was measured at pH 2.0PBS (using NaCl, KCl, Na) containing 100.0. mu. mol/L quercetin2HPO4、KH2PO41 mol/L PBS was prepared, then NaOH and H were used3PO4Adjusting pH), recording a cyclic voltammetry curve under the conditions that the sweep rate is 0.1V/s and the potential interval is-0.2V-0.8V.
As shown in FIG. 11, GCE (curve a) exhibited 1 anodic peak A1 (peak potential at 0.50V, peak current at 5.39 μ A), 2 cathodic peaks C1 and C2 (peak potentials at 0.37V and 0.43V, respectively); the reaction mechanism is that the primary oxidation of the quercetin occurs on the 3, 4-dihydroxy of the B ring, which shows that after 1 electron is transferred to become a quercetin semiquinone free radical, the free radical is unstable and continues to be oxidized into quercetin o-quinone; the quercetin is obtained after two reduction reactions.
A1 peak and a C1 peak appear on ZIF-8@ ZIF-67/GCE (curve b) as well, but the peak current is small, the symmetry is poor, and the ZIF-8@ ZIF-67 with poor conductivity obstructs electron transfer of quercetin on the surface of an electrode and weakens an electric signal of an oxidation peak.
On both Co @ NCNHP/CGE (curve c) and Au-Co @ NCNHP/CGE (curve d), 2 anodic peaks (A1 and A2) appeared, with peak potentials at 0.47V and 0.59V in this order; 3 reduction peaks (C3, C3 'and C3') existed simultaneously, the peak potentials were 0.57V, 0.44V and 0.15V, respectively, while the C1 peak disappeared; the result shows that the quercetin is subjected to stepwise oxidation reaction, specifically, the A1 product is further oxidized and consumed under A2 to completely form quercetin o-quinone, the quercetin o-quinone generates a new product through reactions such as slow desorption, homogeneous isomerization, hydration decomposition and the like, and the product is subjected to reduction reaction during CV back sweep, so that three reduction peaks appear.
Compared with Co @ NCNHP/CGE, the redox peak current on Au-Co @ NCNHP/CGE is obviously increased, the background current is synchronously increased, the peak separation degree is higher, the attribution of each peak can be accurately distinguished, and the analysis of the electrochemical behavior of quercetin is facilitated. This is because the presence of highly conductive nano-Au accelerates the interfacial electron transfer rate and the pore volume of NCNHP increases, providing an open structure that facilitates small molecule adsorption and diffusion.
2. Au-Co @ NCNHP/CGE prepared in example 2 was used as a working electrode (phi 3mm), an Ag/AgCl electrode (saturated KCl solution) was used as a reference electrode, a platinum wire electrode was used as a counter electrode, and electrolyte solutions (NaCl, KCl, Na) containing 100.0. mu. mol/L quercetin at different pH values were used2HPO4、KH2PO41 mol/L PBS was prepared, then NaOH and H were used3PO4Adjusting pH), recording a cyclic voltammetry curve under the conditions that the sweep rate is 0.1V/s and the potential interval is-0.2V-0.8V so as to investigate the influence of the pH value of the electrolyte on the reaction process of the quercetin on the chemical modification electrode.
As shown in FIG. 12, with the increase of pH (1.0-7.0), the oxidation peak potential moves towards the negative direction, indicating that protons participate in the reaction during the oxidation process; the oxidation peak current is maximal at pH 2.0 and the oxidation peak is not significant at pH greater than 6. pK of Quercetina,1About 5.8 when pH>5.8, the quercetin undergoes first-order hydrolysis, the oxidation peak current is reduced, and the peak shape is not obvious. Formula potential of oxidation peak of A1 and reduction peak of C3' (E)0') has a linear relationship with pH, the linear equation is E0The slope of (V) — 0.050pH +0.60(n ═ 7, γ ═ 0.993) was close to the theoretical value (59.0mV), indicating that the redox reaction is a reaction of an equal proton and an equal electron, which is consistent with the electrooxidation characteristics of the phenolic hydroxyl group.
3. The influence of sweep rate on the electrochemical oxidation process was examined by recording cyclic voltammetry curves using Au-Co @ NCNHP/CGE prepared in example 2 as a working electrode (phi 3mm), an Ag/AgCl electrode (saturated KCl solution) as a reference electrode, a platinum wire electrode as a counter electrode, and 100.0 μmol/L quercetin in pH 2.0PBS at a potential interval of-0.2V to 0.8V.
As shown in FIGS. 13A and 13B, in the low sweep speed range (0.01-0.05V/s), the oxidation peaks A1 and A2 exist simultaneously, and the oxidation peaks C3 'and C3' exist simultaneously; one oxidation peak (the superimposed peak of a1 and a2) and 2 reduction peaks (the peaks of C3' and C3 ", the peak of which is weaker at C3") were observed in the medium-high sweep range (more than 0.1V/s); this is attributed to the fact that under the low sweep rate conditions, the semiquinone free radical generated from A1 has enough time to be converted into o-quinone (A2), further isomerized into quercetin p-quinone, and undergo hydration, decomposition, etc. to generate benzofuranone derivatives, dihydroxybenzoic acid, gallic acid, etc., which undergo further reduction reactions (C3' and C3 "). Under the condition of high sweep rate, quercetin has insufficient time to be converted into semiquinone free radical, and directly forms o-quinone (A1 and A2 overlap), and then generates substances (C3 'and C3') such as benzofuranone derivatives, dihydroxybenzoic acid and gallic acid through processes of slow desorption, homogeneous isomerization, hydration decomposition and the like.
In the sweep rate range of 0.1-0.5V/s, the redox peak current (A1 and C3' peaks) has a good linear relationship with the second power of the sweep rate, and as a result, as shown in FIG. 13C, the linear equation can be expressed as Ipa (μ A) being-280.9 upsilon1/2(V/s)1/2+58.55 (n-8, γ -0.995) and Ipc (μ a) -135.5 ν1/2(V/s)1/213.75 (n-8, γ -0.988), which indicates that the reaction process of chemically modifying quercetin on the electrode is a diffusion control process.
In the sweep rate range of 0.25 to 1.0V/s, the peak potential and the logarithm of the sweep rate have a good linear relationship, and as a result, as shown in fig. 13D, the linear regression equations can be expressed as epa (V) ═ 0.073ln υ (V/s) +0.68(n ═ 11, γ ═ 0.986) and epc (V) ═ 0.056ln υ (V/s) +0.73(n ═ 11, γ ═ 0.993), respectively.
4. Working curve of quercetin
In order to measure the response sensitivity of Au-Co @ NCNHP/GCE to the electrooxidation reaction of quercetin, Differential Pulse Voltammetry (DPV) is adopted for testing, Au-Co @ NCNHP/CGE prepared in example 2 is used as a working electrode (phi is 3mm), an Ag/AgCl electrode (saturated KCl solution) is used as a reference electrode, a platinum wire electrode is used as a counter electrode, pH 2.0PBS is used as an electrolyte solution, the potential interval is-0.2V-0.8V, and the sweep rate is 0.1V/s.
As shown in fig. 14, the oxidation peak current (a1) is proportional to the concentration of quercetin in the ranges of 0.05 to 35.0 μmol/L and 35.0 to 80.0 μmol/L, the linear equations are Ipa (μ a) ═ 1.07C (μmol/L) +0.027(n ═ 9, γ ═ 0.997) and Ipa (μ a) ═ 0.54C (μmol/L) +22.75(n ═ 5, γ ═ 0.995), and the detection limit is 0.023 μmol/L (3 σ). compared with the reported chemically modified electrode, Au — Co @ NCNHP/GCE has a wider detection range and a lower detection limit, and the specific comparison results are shown in table 2.
TABLE 2 comparison of quercetin detection results with different chemically modified electrodes
Note: [1] ping X, ZHao F, Zeng B.Voltammetric determination of quercetated a multi-walled carbon nanotubes paste electrode [ J ]. Microchemical Journal,2007,85(2): 244-.
[2]ZhengY.,Ye L.,Yan L.,et al.The electrochemical behavior anddetermination ofquercetin in choline chloride/urea deep eutectic solventelectrolyte based on abrasively immobilized multi-wall carbon nanotubesmodifiedelectrode[J].InternationJournalofElectrochemical Science,2014,9:238-248.
[3]Sun S.,Zhang M.,Li Y.,et al.Amolecularly imprinted polymer withincorporated graphene oxide for electrochemicaldeterminationofquercetin[J].Sensors,2013,13(5):5493-5506.
[4]Oliveira F.C.M.D.,Serrano S.H.P.Electrochemically active L-cysteine gold modified electrodes[J].ElectrochimicaActa,2014,125:566-572.
[5]Zhang Z.F.,Miao Y.M.,Lian L.W.,et al.Detection of quercetin basedon Al3+-amplified phosphorescence signals ofmanganese-dopedZnS quantumdots[J].AnalyticalBiochemistry,2015,489:17-24.
EXAMPLE 4 actual sample determination
To verify the utility and reliability of the differential pulse voltammetry in example 3, Au-Co @ NCNHP/GCE was used for the quantitative detection of quercetin in ginkgo biloba leaves and onions using a standard addition method.
The sample treatment process was carried out by cutting onion, weighing 5.0g, grinding to paste, transferring to 50m L ethanol for 40min, then centrifuging the mixture (4000r/min) for 10min, and finally diluting 1.0m L supernatant with PBS (pH 2.0) to 10.0m L for electrochemical assay.
Ginkgo biloba pieces were purchased from a local pharmacy (Haikouqi pharmaceutical Co., Ltd., Z20053069), 2 ginkgo biloba leaves were first ground into powder, sonicated in 10m L ethanol for 10min, the mixture was then filtered, diluted with ethanol to 50m L, and added to an electrolyte solution for electrochemical assay.
The detection results are shown in table 3, the recovery rate of the onion sample is between 98.73% and 102.5%, and the recovery rate of the ginkgo leaves is between 97.96% and 101.9%. The result shows that Au-Co @ NCNHP/GCE can be used for content analysis of quercetin in different samples.
TABLE 3 measurement results of quercetin content in actual samples
The general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The preparation method of the gold-cobalt @ nitrogen doped carbon nanotube hollow polyhedron is characterized by comprising the following steps of:
(1) preparation of ZIF-8@ ZIF-67
Taking ZIF-8 as an inner core, and epitaxially growing ZIF-67 on the ZIF-8 to obtain ZIF-8@ ZIF-67;
(2) preparation of Co @ NCNHP
Calcining ZIF-8@ ZIF-67 under protective gas, and soaking the calcined material with acid to remove surface metal oxide to obtain Co @ NCNHP;
(3) preparation of Au-Co @ NCNHP
And loading the gold nanoparticles on the Co @ NCNHP under ice bath to obtain Au-Co @ NCNHP.
2. The method for preparing the gold-cobalt @ nitrogen doped carbon nanotube hollow polyhedron of claim 1, wherein,
the step (1) is as follows:
1) preparation of ZIF-8
Respectively dissolving soluble zinc salt and 2-methylimidazole in methanol to obtain a solution I and a solution II;
dropwise adding the solution II into the solution I, stirring, carrying out solid-liquid separation, washing and drying to obtain a ZIF-8 crystal;
2) preparation of ZIF-8@ ZIF-67
Dispersing ZIF-8 in methanol to obtain ZIF-8 suspension;
respectively dissolving soluble cobalt salt and 2-methylimidazole in methanol to obtain a solution III and a solution IV;
adding the solution III into the ZIF-8 suspension to obtain a mixed solution;
and adding the solution IV into the mixed solution, stirring, carrying out solid-liquid separation, washing and drying to obtain ZIF-8@ ZIF-67.
3. The method for preparing the gold-cobalt @ nitrogen doped carbon nanotube hollow polyhedron of claim 2, wherein,
in the step 1), the step (A) is carried out,
the soluble zinc salt comprises one or more of zinc nitrate, zinc sulfate or zinc acetate;
the mol ratio of the soluble zinc salt to the 2-methylimidazole is 1: 3-5;
dropwise adding the solution II into the solution I, stirring for 20-36h, centrifuging at 10000-;
in the step 2), the step (c) is carried out,
the soluble cobalt salt comprises one or more of cobalt nitrate, cobalt sulfate or cobalt acetate;
the dosage ratio of ZIF-8, soluble cobalt salt and 2-methylimidazole is 1 g: 0.03-0.05 mol: 0.1-0.25 mol;
after the solution four is added into the mixed solution, the stirring time is 20-36h, the centrifugation speed is 10000-13000r/min, and the drying temperature is 50-80 ℃.
4. The method for preparing the gold-cobalt @ nitrogen doped carbon nanotube hollow polyhedron of claim 1, wherein,
the step (2) is specifically as follows:
calcining ZIF-8@ ZIF-67 at 915 ℃ and 950 ℃ for 3-5h by taking argon or nitrogen as protective gas;
cooling the material obtained by calcination in H2SO4Soaking in the solution, carrying out solid-liquid separation, and washing to obtain Co @ NCNHP;
the temperature rise rate before calcination does not exceed 5 ℃/min;
H2SO4the concentration of the solution is 0.7-0.9 mol/L, and the soaking time is 10-14 h.
5. The method for preparing the gold-cobalt @ nitrogen doped carbon nanotube hollow polyhedron of claim 1, wherein,
the step (3) is specifically as follows:
dispersing Co @ NCNHP in an ethanol-water solution under ice bath, adding a chloroauric acid water solution, and stirring for 3-5 h; addition of NaBH was continued4Stirring the aqueous solution for reaction, wherein the stirring time is not more than 1h, and the stirring speed is not more than 2000 r/min; after the reaction, carrying out solid-liquid separation, washing and drying to obtainAu-Co@NCNHP；
The volume fraction of ethanol in the ethanol-water solution is 25-50%;
co @ NCNHP, chloroauric acid in aqueous chloroauric acid solution, NaBH4NaBH in aqueous solution4The dosage ratio is 1 mg: 6-40 μ g: 1-8 mu mol.
6. Use of the gold-cobalt @ nitrogen doped carbon nanotube hollow polyhedron prepared by the preparation method of any one of claims 1 to 5 in preparation of an electrochemical sensor.
7. The application of the gold-cobalt @ nitrogen doped carbon nanotube hollow polyhedron prepared by the preparation method of any one of claims 1 to 5 in preparing a chemically modified electrode.
8. A chemically modified electrode, characterized in that,
modifying a gold-cobalt @ nitrogen doped carbon nanotube hollow polyhedron on the surface of an electrode material, wherein the gold-cobalt @ nitrogen doped carbon nanotube hollow polyhedron is prepared by the preparation method of any one of claims 1 to 5.
9. The use of the gold-cobalt @ nitrogen doped carbon nanotube hollow polyhedron prepared by the preparation method of any one of claims 1 to 5 or the chemically modified electrode of claim 8 in quercetin detection.
10. A method for detecting quercetin is characterized in that,
the method comprises the steps of taking the chemically modified electrode as a working electrode, drawing a quercetin measurement standard curve by adopting a differential pulse voltammetry method, and measuring the content of quercetin in a sample to be measured by a standard addition method.
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