CN114959770A - Preparation method and application of bimetallic ion doped carbon quantum dot catalyst - Google Patents
Preparation method and application of bimetallic ion doped carbon quantum dot catalyst Download PDFInfo
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- CN114959770A CN114959770A CN202210722224.8A CN202210722224A CN114959770A CN 114959770 A CN114959770 A CN 114959770A CN 202210722224 A CN202210722224 A CN 202210722224A CN 114959770 A CN114959770 A CN 114959770A
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 177
- 239000003054 catalyst Substances 0.000 title claims abstract description 165
- 238000002360 preparation method Methods 0.000 title claims abstract description 51
- 150000002500 ions Chemical class 0.000 claims abstract description 108
- 239000010411 electrocatalyst Substances 0.000 claims abstract description 65
- 239000001509 sodium citrate Substances 0.000 claims abstract description 54
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 54
- 229910052751 metal Inorganic materials 0.000 claims abstract description 43
- 239000002184 metal Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 37
- 230000004913 activation Effects 0.000 claims abstract description 37
- 239000004202 carbamide Substances 0.000 claims abstract description 37
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 37
- 150000003839 salts Chemical class 0.000 claims abstract description 28
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 27
- 230000003197 catalytic effect Effects 0.000 claims abstract description 11
- 238000011065 in-situ storage Methods 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 67
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 58
- 239000007864 aqueous solution Substances 0.000 claims description 58
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 44
- 238000001994 activation Methods 0.000 claims description 37
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 29
- 229910052709 silver Inorganic materials 0.000 claims description 29
- 239000004332 silver Substances 0.000 claims description 29
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 29
- 238000002484 cyclic voltammetry Methods 0.000 claims description 26
- 229910052697 platinum Inorganic materials 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 17
- 238000011068 loading method Methods 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 17
- 239000006228 supernatant Substances 0.000 claims description 17
- 238000007605 air drying Methods 0.000 claims description 16
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 10
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 10
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 10
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 claims description 8
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 7
- 238000003487 electrochemical reaction Methods 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 18
- 239000003792 electrolyte Substances 0.000 description 18
- 239000001257 hydrogen Substances 0.000 description 18
- 229910052739 hydrogen Inorganic materials 0.000 description 18
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 15
- 239000001301 oxygen Substances 0.000 description 15
- 229910052760 oxygen Inorganic materials 0.000 description 15
- 230000002441 reversible effect Effects 0.000 description 15
- 239000012530 fluid Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 10
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 description 5
- BDQVVKMTUBGARP-UHFFFAOYSA-N [Cs].[Pt] Chemical compound [Cs].[Pt] BDQVVKMTUBGARP-UHFFFAOYSA-N 0.000 description 4
- OSOVKCSKTAIGGF-UHFFFAOYSA-N [Ni].OOO Chemical compound [Ni].OOO OSOVKCSKTAIGGF-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- OUFGXIPMNQFUES-UHFFFAOYSA-N molybdenum ruthenium Chemical compound [Mo].[Ru] OUFGXIPMNQFUES-UHFFFAOYSA-N 0.000 description 4
- 229910000483 nickel oxide hydroxide Inorganic materials 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229910000570 Cupronickel Inorganic materials 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- HSSJULAPNNGXFW-UHFFFAOYSA-N [Co].[Zn] Chemical compound [Co].[Zn] HSSJULAPNNGXFW-UHFFFAOYSA-N 0.000 description 3
- PCEXQRKSUSSDFT-UHFFFAOYSA-N [Mn].[Mo] Chemical compound [Mn].[Mo] PCEXQRKSUSSDFT-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 description 3
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 3
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 3
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 3
- ZMCCBULBRKMZTH-UHFFFAOYSA-N molybdenum platinum Chemical compound [Mo].[Pt] ZMCCBULBRKMZTH-UHFFFAOYSA-N 0.000 description 3
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 3
- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical compound [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- 230000010757 Reduction Activity Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000002059 diagnostic imaging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 150000002678 macrocyclic compounds Chemical class 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/065—Carbon
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The invention discloses a preparation method of a bimetallic ion doped carbon quantum dot catalyst, which comprises the following steps: sodium citrate is used as a precursor carbon source, urea is used as a nitrogen source, metal salt is used as a catalytic active metal source, and the bimetallic ion doped carbon quantum dot catalyst is obtained in one step through a hydrothermal reaction; further, the bimetallic doped carbon quantum dot electrocatalyst is obtained by an in-situ activation method in the electrochemical reaction process. The method is simple to operate, low in cost, green and environment-friendly in preparation process, and easy to realize large-scale preparation.
Description
Technical Field
The invention belongs to the technical field of electrocatalyst preparation, and particularly relates to a preparation method and application of a bimetallic ion doped carbon quantum dot catalyst.
Background
The electrocatalysis technology is a new emerging means, low value-added products are converted into high value-added products by utilizing clean electric energy, and the rapid development of the electrocatalysis technology in recent years has important significance for pursuing low carbon economy in the society of the current and realizing the goals of carbon neutralization and carbon peak reaching. The high-efficiency electrocatalysis technology such as electrocatalysis oxygen reduction technology, electrocatalysis hydrogen evolution technology, electrocatalysis oxygen evolution technology, electrocatalysis carbon dioxide reduction technology, electrocatalysis ammonia synthesis technology and the like are all based on the design and synthesis of high-efficiency electrocatalysts. Therefore, how to design and develop an inexpensive and efficient electrocatalyst is a key research content in the field of electrocatalysis today.
The core of the development of the high-efficiency electrocatalyst comprises two aspects, namely the design of the catalytic site and the selection of a carrier of the catalytic site. The carbon-based material has excellent conductivity, and ensures the rapid conduction of electrons in the electrocatalysis process; while having a rich abundance of heteroatoms or defect sites that may serve to anchor the metal catalytic sites, are generally preferred as catalyst supports. For example, in the preparation of a supported non-noble metal electrocatalyst with MIL-88 as a carrier and the application thereof in oxygen reduction reaction (publication No. CN113555564A), it is mentioned that a metal macrocyclic compound and a metal organic framework material MIL-88 are assembled and precipitated in situ, and a carbon-coated iron-based electrocatalyst can be obtained after heat treatment at a high temperature of 500 ℃ to 1000 ℃, and has good electrocatalytic oxygen reduction activity. However, the high temperature heat treatment step involved in this method is a highly energy-consuming process, which is not conducive to further large-scale industrial production. Meanwhile, in a carbon material-supported platinum catalyst, a preparation method and application thereof (publication No. CN113363515A), a carbon black material and a platinum precursor solution are complexed through a complexing agent, and a sodium borohydride reducing agent is added under an inert atmosphere for reduction to obtain the carbon material-supported platinum catalyst. Although the method does not need the energy-consuming process of high-temperature heat treatment, the synthesis conditions are harsh, the operation is complicated, and the method is not beneficial to subsequent further industrial application. On the other hand, most of the existing catalysts only adopt one metal, and the synergistic effect of the bimetal is more beneficial to exerting the catalytic activity. Therefore, it is a great challenge in the field of electrocatalysis to develop a high-efficiency bimetallic supported carbon-based catalyst and synchronously develop a green and high-efficiency synthetic method suitable for large-scale industrial production.
As a traditional semiconductor material, the carbon quantum dots have wide application in the fields of medical imaging, chemical sensors and the like due to the outstanding charge transmission capacity and light stability, have the advantages of good water solubility, low toxicity, environmental friendliness, low cost and the like, and are easy to realize large-scale preparation. Importantly, the carbon quantum dots have abundant defect sites and a large number of functional group modifications, and can well anchor various metal catalytic sites. Therefore, the catalyst has great potential in the preparation of novel catalysts, particularly novel electrocatalysts, but reports on the bimetallic-based catalyst based on carbon quantum dots and a preparation method thereof are not available.
Disclosure of Invention
The invention aims to provide a preparation method of a bimetallic ion doped carbon quantum dot catalyst.
Another object of the present invention is to provide a method for preparing a bimetal doped carbon quantum dot electrocatalyst by using the bimetal ion doped carbon quantum dot catalyst.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of a bimetallic ion doped carbon quantum dot catalyst, which comprises the following steps: the bimetallic ion doped carbon quantum dot catalyst is obtained by one step of hydrothermal reaction by using sodium citrate as a precursor carbon source, urea as a nitrogen source and metal salt as a catalytic active metal source.
The metal in the metal salt is selected from iron, nickel, cobalt, zinc, copper, manganese, molybdenum, cesium, platinum and ruthenium; the metal salt is selected from nitrate, chloride, sulfate and acetate of the above metals; further selected from the group consisting of ferric nitrate, nickel nitrate, cobalt nitrate, zinc nitrate, copper nitrate, manganese nitrate, molybdenum nitrate, cesium nitrate, platinum chloride, and ruthenium chloride.
The preparation method of the bimetallic ion doped carbon quantum dot catalyst comprises the following steps:
dissolving sodium citrate and urea with a molar ratio of (0.125-8): 1 in deionized water, wherein the addition amount of the deionized water is 20-100 mL, and simultaneously adding two different metal salt solutions with the concentration of 50-150 gL respectively in an amount of 0.1-1 mL –1 Stirring the two different metal salts at a molar ratio of (0.25-4) to 1 at room temperature for 5-20 min to obtain a clear transparent solution; the molar ratio of the sodium citrate to the total amount of the two different metal salts is (20-150): 1;
and transferring the solution into a hydrothermal reaction kettle, reacting for 2-12 h at the temperature of 120-200 ℃, cooling to room temperature, centrifuging the obtained black solution, and taking supernatant to obtain the aqueous solution of the bimetallic ion doped carbon quantum dot catalyst.
The solid content of the bimetallic ion doped carbon quantum dot catalyst aqueous solution is 15-50 g/L.
A second aspect of the present invention provides a method for preparing a bimetal doped carbon quantum dot electrocatalyst using the bimetal ion doped carbon quantum dot catalyst.
The method comprises the following steps:
directly coating the bimetallic ion doped carbon quantum dot catalyst aqueous solution on hydrophilic carbon paper, and directly obtaining a catalyst working electrode after natural air drying; and (2) carrying out electrochemical cyclic voltammetry in-situ activation in a potassium hydroxide solution by adopting a three-electrode system, taking a silver/silver chloride electrode as a reference electrode and a platinum sheet electrode as a counter electrode to obtain the bimetallic doped carbon quantum dot electrocatalyst.
The load capacity of the bimetallic ion doped carbon quantum dot catalyst is 0.1-2L/m 2 。
The concentration of the potassium hydroxide solution is 0.1-1mol L –1 The scanning voltage range of the cyclic voltammetry is 0V-1V; the scanning rate is 10-100 mV s –1 (ii) a The cycle times are 10-100 circles.
The bimetallic doped carbon quantum dot electrocatalyst can be applied to electrocatalytic reactions including but not limited to oxygen evolution reaction, electrocatalytic hydrogen evolution reaction, electrocatalytic carbon dioxide reduction reaction and the like.
Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:
the invention synthesizes the bimetallic ion doped carbon quantum dot catalyst with uniform and stable properties by a simple one-step hydrothermal method; and further obtaining the bimetallic doped carbon quantum dot electrocatalyst by a cyclic voltammetry in-situ activation method. No calcining high-temperature energy-consuming treatment step or adding a highly corrosive sodium borohydride reducing agent. The preparation process is simple in process, green and environment-friendly, low in cost and easy to realize industrialization.
According to the invention, sodium citrate and urea are used as precursors, and the surface of the bimetallic ion doped carbon quantum dot catalyst prepared by a hydrothermal method has rich functional groups such as hydroxyl, carboxyl, amino and the like, so that rich sites can be provided for the adsorption of metal ions, and the stability and activity of the bimetallic ion doped carbon quantum dot catalyst are ensured. Meanwhile, the bimetallic ions have a synergistic catalytic effect, so that the catalytic activity of the catalyst can be further improved.
The method can generate the high-efficiency bimetallic doped carbon quantum dot electrocatalyst in situ in the process of activating the bimetallic ion doped carbon quantum dot catalyst by the electrochemical cyclic voltammetry. And because the bimetallic ion doped carbon quantum dot catalyst has abundant carbon defect sites, the size of bimetallic-based active species can be effectively controlled in the activation process of the electrochemical cyclic voltammetry, and the uniform distribution of the bimetallic-based active species on the carbon quantum dot carrier is also ensured.
The bimetallic doped carbon quantum dot electrocatalyst prepared by the method is far superior to the commercial electrocatalyst and the electrocatalyst prepared by other traditional methods (pyrolysis method and the like) in catalytic systems such as oxygen evolution reaction, electrocatalytic hydrogen evolution reaction, electrocatalytic carbon dioxide reduction reaction and the like.
The method is simple to operate, low in cost, green and environment-friendly in preparation process, and easy to realize large-scale preparation.
In conclusion, urea and sodium citrate are used as precursors, so that the raw materials are easy to obtain and the cost is low; water is used as a solvent, and the post-treatment is simple and pollution-free; because the carbon quantum contains a large amount of N, O heteroatom functional groups, the metal ion loading efficiency is high, and the dosage is small (10-300 mg/g); and secondly, the obtained bimetallic ion doped carbon quantum dot aqueous solution can be directly added to hydrophilic carbon paper to prepare an electrode, and an ultrasonic dispersion step and a binder addition step which are required in the traditional powder electrocatalyst loading process are not needed, so that the time and the labor are saved. And thirdly, the electrochemical cyclic voltammetry activation method adopted by the invention is simple to operate, and can quickly activate the bimetallic ion doped carbon quantum dots into the bimetallic doped carbon quantum dot electrocatalyst under the conditions of normal temperature and normal pressure. Finally, the overpotential of the oxygen evolution reaction can be as low as 200mV (the current density is 10mA cm) -2 And (c) is far superior to commercial ruthenium dioxide (RuO) 2 ) Catalyst (31)0mV) and an iridium/carbon (Ir/C) catalyst (270 mV).
Drawings
FIG. 1 shows a bimetallic ion doped carbon quantum dot catalyst aqueous solution with uniform and stable properties prepared by a hydrothermal method.
Fig. 2 is a transmission electron micrograph (a) and a partial enlarged view (b) of a bimetallic ion doped carbon quantum dot catalyst aqueous solution prepared by a hydrothermal method.
Fig. 3 is a transmission electron micrograph (a) and a partial enlarged view (b) of the bimetallic doped quantum dot electrocatalyst after in-situ activation by cyclic voltammetry, wherein in the view of b, the lattice spacing d is 0.233nm, and the corresponding bimetallic active species is the 101 crystal face of iron-doped nickel oxyhydroxide.
Fig. 4 is a scanning electron microscope image of the cross section of bare carbon paper (a) and carbon paper (b) loaded with the bimetallic doped carbon quantum dot catalyst.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
For a better understanding of the invention, and not as a limitation on the scope thereof, all numbers expressing quantities, percentages, and other numerical values used in this application are to be understood as being modified in all instances by the term "about". Accordingly, unless expressly indicated otherwise, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
The following examples describe in more detail the preparation of the dual metal ion doped carbon quantum dot catalyst by a hydrothermal method based on 10 metal salts of fe, co, ni, cu, zn, mn, mo, cs, pt, ru, and the preparation of the dual metal doped carbon quantum dot electrocatalyst by an electrochemical cyclic voltammetry in situ activation method, respectively. The performance parameters of the catalyst are determined by the overpotential of the oxygen evolution reaction, and the lower the value, the better the value.
Example 1
A preparation method of a bimetallic ion doped carbon quantum dot catalyst comprises the following steps: sodium citrate (0.038mol, 10g) and urea (0.049mol, 3g) were dissolved in 50ml of deionized water, while ferric nitrate solution (100mg ml) was added –1 ) And nickel nitrate solution (100mg ml) –1 ) 0.5ml each, the molar ratio of sodium citrate to urea is 0.78:1, the molar ratio of ferric nitrate to nickel nitrate is 0.76:1, and the molar ratio of sodium citrate to the total amount of the two different metal salts is 79: 1; stirring at room temperature for 15min to obtain a clear and transparent solution.
Transferring the mixture into a 150ml hydrothermal reaction kettle, reacting for 2 hours at 120 ℃, cooling to room temperature, centrifuging the obtained black solution, and taking supernatant fluid, namely the iron-nickel bimetallic ion doped carbon quantum dot catalyst aqueous solution with uniform and stable shape.
As shown in fig. 1 and fig. 2, fig. 1 shows that the bimetallic ion doped carbon quantum dot catalyst aqueous solution prepared by the hydrothermal method and having uniform and stable properties has excellent dispersibility in water. Fig. 2 is a transmission electron micrograph (a) and a partial enlarged view (b) of a bimetallic ion doped carbon quantum dot catalyst aqueous solution prepared by a hydrothermal method. As can be seen from a in FIG. 2, the obtained catalyst has a one-dimensional dot-shaped morphology with a diameter of about 5 nm. As can be seen from b in fig. 2, the obtained catalyst has regular lattice fringes, the lattice spacing of which is 0.28nm, corresponding to the (020) plane of carbon, and thus fig. 2 demonstrates the successful synthesis of the carbon quantum dot aqueous solution; and analyzing by combining with Inductively Coupled Plasma (ICP) to obtain that the mass fractions of iron and nickel in the carbon quantum dot catalyst aqueous solution are respectively 1.1% and 1.6%. In conclusion, the iron-nickel bimetallic ion doped carbon quantum dot catalyst can be successfully obtained.
A preparation method of a bimetallic doped carbon quantum dot electrocatalyst comprises the following steps: directly dripping 40uL of the obtained iron-nickel bimetallic ion doped carbon quantum dot catalyst aqueous solution on hydrophilic carbon paper, wherein the loading capacity of the bimetallic ion doped carbon quantum dot catalyst is 0.4L/m 2 (ii) a The solid content of the bimetallic ion doped carbon quantum dot catalyst aqueous solution is 27 g/L. Can be directly used as a catalyst after being naturally air-driedWorking electrode, platinum sheet electrode as counter electrode, silver/silver chloride electrode as reference electrode, in 1mol L –1 The potassium hydroxide electrolyte is activated by cyclic voltammetry, and the scanning voltage range is 0V-1V (relative to a reversible hydrogen electrode); the scanning speed is 100mV/s, the number of scanning circles is 10 circles, and the iron-nickel bimetallic doped carbon quantum dot electrocatalyst is obtained after activation.
Fig. 3 is a transmission electron microscope (a) and a partial enlarged view (b) of the iron-nickel bimetal doped carbon quantum dot electrocatalyst activated in situ by cyclic voltammetry, wherein the lattice spacing d in b is 0.233nm, which corresponds to the 101 crystal plane of iron-doped nickel oxyhydroxide. Fig. 4 is a scanning electron microscope image of the cross section of bare carbon paper (a) and carbon paper (b) loaded with the bimetallic doped carbon quantum dot catalyst. As can be seen from a in fig. 3, the electrocatalyst after electrochemical activation still maintains a one-dimensional dotted morphology with a size of about 5nm, indicating that the carbon quantum dots themselves do not change before and after electrochemical activation. But the surface of the material shows a plurality of black clusters which are uniformly distributed, the diameter of the black clusters is about 1.5nm, and new species are formed. As can be seen from b in fig. 3, the lattice spacing of the clusters appearing after electrochemical activation was 0.233nm, corresponding to the (101) plane of the iron-doped nickel oxyhydroxide. In summary, it can be concluded that the electrochemical activation step activates the iron-nickel bimetallic ion-doped carbon quantum dot catalyst into an iron-nickel bimetallic doped carbon quantum dot electrocatalyst, wherein the bimetallic-based active species is iron-doped nickel oxyhydroxide. Fig. 4 illustrates the uniform distribution of the bi-metal ion doped carbon quantum dot catalyst on the carbon paper.
Electrocatalytic oxygen evolution activity of the bimetallic doped carbon quantum dot electrocatalyst:
the prepared iron-nickel bimetallic doped carbon quantum dot electrocatalyst is applied to potassium hydroxide electrolyte (1mol L) -1 ) The overpotential of the medium oxygen evolution reaction is 200mV, which is far superior to that of the commercial RuO 2 Catalyst (310mV) and iron-nickel bimetallic-based electrocatalyst (250mV) prepared by other methods (Chem Catalysis 1, 734-745, August 19,2021, operating method of electrocatalytic oxygen evolution test is consistent with the literature report).
Example 2
Preparation of bimetallic ion doped carbon quantum dot catalystThe method comprises the following steps: sodium citrate (0.038mol, 10g) and urea (0.049mol, 3g) were dissolved in 50ml of deionized water, while adding ferric nitrate solution (100mg ml) –1 ) And cobalt nitrate solution (100mg ml) –1 ) 0.5ml each, the molar ratio of sodium citrate to urea is 0.78:1, the molar ratio of ferric nitrate to cobalt nitrate is 0.76:1, and the molar ratio of sodium citrate to the total amount of the two different metal salts is 79: 1; stirring at room temperature for 15min to obtain a clear and transparent solution.
Transferring the mixture into a 150ml hydrothermal reaction kettle, reacting for 2 hours at 120 ℃, cooling to room temperature, centrifuging the obtained black solution, and taking supernatant fluid, namely the iron-cobalt bimetallic ion doped carbon quantum dot catalyst aqueous solution with uniform and stable shape.
A preparation method of a bimetallic doped carbon quantum dot electrocatalyst comprises the following steps: directly dripping 40uL of the obtained iron-cobalt bimetallic ion doped carbon quantum dot catalyst aqueous solution on hydrophilic carbon paper, wherein the loading capacity of the bimetallic ion doped carbon quantum dot catalyst is 0.4L/m 2 (ii) a The solid content of the bimetallic ion doped carbon quantum dot catalyst aqueous solution is 27 g/L. After natural air drying, the catalyst can be directly used as a catalyst working electrode, a platinum sheet electrode is used as a counter electrode, a silver/silver chloride electrode is used as a reference electrode, and the concentration of the silver/silver chloride electrode is 1mol L –1 The potassium hydroxide electrolyte is activated by cyclic voltammetry, and the scanning voltage range is 0V-1V (relative to a reversible hydrogen electrode); the scanning rate was 100mV/s, and the number of scanning cycles was 10 cycles. And obtaining the iron-cobalt bimetallic doped carbon quantum dot electrocatalyst after activation.
Electrocatalytic oxygen evolution activity of the bimetallic doped carbon quantum dot electrocatalyst:
the prepared iron-cobalt bimetallic doped carbon quantum dot electrocatalyst is placed in potassium hydroxide electrolyte (1mol L) -1 ) The overpotential of the oxygen evolution reaction is 220mV which is far superior to that of the commercial RuO 2 Catalyst (310mV) and an iron-cobalt bimetallic based electrocatalyst (295mV) prepared by other methods (adv. Funct. Mater.2020, 1909889).
Example 3
A preparation method of a bimetallic ion doped carbon quantum dot catalyst comprises the following steps: sodium citrate (0.038mol, 10g) and urea (0.049mol, 3g) were dissolved in 50ml for deionizationIn water, cobalt nitrate solution (100mg ml) was added simultaneously –1 ) And nickel nitrate solution (100mg ml) –1 ) 0.5ml each, the molar ratio of sodium citrate to urea is 0.78:1, the molar ratio of cobalt nitrate to nickel nitrate is 1:1, and the molar ratio of sodium citrate to the total amount of the two different metal salts is 69: 1; stirring at room temperature for 15min to obtain a clear and transparent solution.
Transferring the cobalt-nickel bimetallic ion doped carbon quantum dot catalyst into a 150ml hydrothermal reaction kettle, reacting for 2h at 120 ℃, cooling to room temperature, centrifuging the obtained black solution, and taking supernatant, namely the cobalt-nickel bimetallic ion doped carbon quantum dot catalyst aqueous solution with uniform and stable shape.
A preparation method of a bimetallic doped carbon quantum dot electrocatalyst comprises the following steps: directly dripping 40uL of the obtained cobalt-nickel bimetallic ion doped carbon quantum dot catalyst aqueous solution on hydrophilic carbon paper, wherein the loading capacity of the bimetallic ion doped carbon quantum dot catalyst is 0.4L/m 2 (ii) a The solid content of the bimetallic ion doped carbon quantum dot catalyst aqueous solution is 27 g/L. After natural air drying, the catalyst can be directly used as a catalyst working electrode, a platinum sheet electrode is used as a counter electrode, a silver/silver chloride electrode is used as a reference electrode, and the concentration of the silver/silver chloride electrode is 1mol L –1 The activation is carried out in the potassium hydroxide electrolyte by cyclic voltammetry, the scanning voltage range is 0V-1V (relative to a reversible hydrogen electrode), the scanning speed is 100mV/s, the number of scanning cycles is 10 cycles, and the cobalt-nickel bimetallic doped carbon quantum dot electrocatalyst is obtained after the activation.
Electrocatalytic oxygen evolution activity of the bimetallic doped carbon quantum dot electrocatalyst:
the prepared cobalt-nickel bimetallic doped carbon quantum dot electrocatalyst is placed in potassium hydroxide electrolyte (1mol L) -1 ) The overpotential of the oxygen evolution reaction is 220mV which is far superior to that of the commercial RuO 2 Catalyst (310mV) and cobalt-nickel bimetallic doped electrocatalyst (350mV) prepared by other methods (ACS appl. Mater. interfaces 2021,13, 45394-45405).
Example 4
A preparation method of a bimetallic ion doped carbon quantum dot catalyst comprises the following steps: sodium citrate (0.038mol, 10g) and urea (0.049mol, 3g) were dissolved in 50ml of deionized water, while zinc nitrate solution (100mg ml) was added –1 ) And cobalt nitrate solution (100mg ml) –1 ) 0.5ml each, the molar ratio of sodium citrate to urea is 0.78:1, the molar ratio of zinc nitrate to cobalt nitrate is 0.96: 1, the molar ratio of sodium citrate to the total amount of two different metal salts is 71: 1; stirring at room temperature for 15min to obtain a clear and transparent solution.
Transferring the mixture into a 150ml hydrothermal reaction kettle, reacting for 2 hours at 120 ℃, cooling to room temperature, centrifuging the obtained black solution, and taking supernatant fluid, namely the zinc-cobalt bimetallic ion doped carbon quantum dot catalyst aqueous solution with uniform and stable shape.
A preparation method of a bimetallic doped carbon quantum dot electrocatalyst comprises the following steps: directly dripping 40uL of the obtained zinc-cobalt bimetallic ion doped carbon quantum dot catalyst aqueous solution on hydrophilic carbon paper, wherein the loading capacity of the bimetallic ion doped carbon quantum dot catalyst is 0.4L/m 2 (ii) a The solid content of the bimetallic ion doped carbon quantum dot catalyst aqueous solution is 27 g/L. After natural air drying, the catalyst can be directly used as a catalyst working electrode, a platinum sheet electrode is used as a counter electrode, a silver/silver chloride electrode is used as a reference electrode, and the concentration of the silver/silver chloride electrode is 1mol L –1 The activation is carried out in the potassium hydroxide electrolyte by cyclic voltammetry, the scanning voltage range is 0V-1V (relative to a reversible hydrogen electrode), the scanning speed is 100mV/s, the number of scanning cycles is 10 cycles, and the zinc-cobalt bimetal doped carbon quantum dot electrocatalyst is obtained after the activation.
Example 5
A preparation method of a bimetallic ion doped carbon quantum dot catalyst comprises the following steps: sodium citrate (0.038mol, 10g) and urea (0.049mol, 3g) were dissolved in 50ml of deionized water, while zinc nitrate solution (100mg ml) was added –1 ) And nickel nitrate solution (100mg ml) –1 ) 0.5ml each, the molar ratio of sodium citrate to urea is 0.78:1, the molar ratio of zinc nitrate to nickel nitrate is 0.96: 1, the molar ratio of sodium citrate to the total amount of two different metal salts is 71: 1; stirring at room temperature for 15min to obtain a clear and transparent solution.
Transferring the mixture into a 150ml hydrothermal reaction kettle, reacting for 2 hours at 120 ℃, cooling to room temperature, centrifuging the obtained black solution, and taking supernatant fluid, namely the zinc-nickel bimetallic ion doped carbon quantum dot catalyst aqueous solution with uniform and stable shape.
A preparation method of a bimetallic doped carbon quantum dot electrocatalyst comprises the following steps: 40uL of the obtained zinc-nickel bimetallic ion doped carbon quantum dot catalyst aqueous solution is directly dripped on hydrophilic carbon paper, and the loading capacity of the bimetallic ion doped carbon quantum dot catalyst is 0.4L/m 2 (ii) a The solid content of the bimetallic ion doped carbon quantum dot catalyst aqueous solution is 27 g/L. After natural air drying, the catalyst can be directly used as a catalyst working electrode, a platinum sheet electrode is used as a counter electrode, a silver/silver chloride electrode is used as a reference electrode, and the concentration of the silver/silver chloride electrode is 1mol L –1 The activation is carried out in the potassium hydroxide electrolyte by cyclic voltammetry, the scanning voltage range is 0V-1V (relative to a reversible hydrogen electrode), the scanning speed is 100mV/s, the number of scanning cycles is 10 cycles, and the zinc-nickel bimetallic doped carbon quantum dot electrocatalyst is obtained after the activation.
Example 6
A preparation method of a bimetallic ion doped carbon quantum dot catalyst comprises the following steps: sodium citrate (0.038mol, 10g) and urea (0.049mol, 3g) were dissolved in 50ml of deionized water, while copper nitrate solution (100mg ml) was added –1 ) And nickel nitrate solution (100mg ml) –1 ) 0.5ml each, the molar ratio of sodium citrate to urea is 0.78:1, the molar ratio of copper nitrate to nickel nitrate is 0.97: 1, the molar ratio of sodium citrate to the total amount of two different metal salts is 70: 1; stirring at room temperature for 15min to obtain a clear and transparent solution.
Transferring the mixture into a 150ml hydrothermal reaction kettle, reacting for 2 hours at 120 ℃, cooling to room temperature, centrifuging the obtained black solution, and taking supernatant fluid, namely the uniform and stable copper-nickel bimetallic ion doped carbon quantum dot catalyst aqueous solution.
A preparation method of a bimetallic doped carbon quantum dot electrocatalyst comprises the following steps: directly dripping 40uL of the obtained aqueous solution of the copper-nickel bimetallic ion doped carbon quantum dot catalyst on hydrophilic carbon paper, wherein the loading capacity of the bimetallic ion doped carbon quantum dot catalyst is 0.4L/m 2 (ii) a The solid content of the bimetallic ion doped carbon quantum dot catalyst aqueous solution is 27 g/L. After natural air drying, the catalyst can be directly used as a catalyst working electrode, a platinum sheet electrode is used as a counter electrode, and a silver/silver chloride electrode is used as a reference electrodeVery much, at 1mol L –1 The activation is carried out in the potassium hydroxide electrolyte by cyclic voltammetry, the scanning voltage range is 0V-1V (relative to a reversible hydrogen electrode), the scanning speed is 100mV/s, the number of scanning cycles is 10 cycles, and the copper-nickel bimetal doped carbon quantum dot electrocatalyst is obtained after the activation.
Example 7
A preparation method of a bimetallic ion doped carbon quantum dot catalyst comprises the following steps: sodium citrate (0.038mol, 10g) and urea (0.049mol, 3g) were dissolved in 50ml of deionized water, while adding ferric nitrate solution (100mg ml) –1 ) And zinc nitrate solution (100mg ml) –1 ) 0.5ml each, the molar ratio of sodium citrate to urea is 0.78:1, the molar ratio of the ferric nitrate to the zinc nitrate is 0.78:1, the molar ratio of sodium citrate to the total amount of two different metal salts is 81: 1; stirring at room temperature for 15min to obtain a clear and transparent solution.
Transferring the mixture into a 150ml hydrothermal reaction kettle, reacting for 2 hours at 120 ℃, cooling to room temperature, centrifuging the obtained black solution, and taking supernatant fluid, namely the iron-zinc bimetallic ion doped carbon quantum dot catalyst aqueous solution with uniform and stable shape.
A preparation method of a bimetallic doped carbon quantum dot electrocatalyst comprises the following steps: directly dripping 40uL of the obtained iron-zinc bimetallic ion doped carbon quantum dot catalyst aqueous solution on hydrophilic carbon paper, wherein the load capacity of the bimetallic ion doped carbon quantum dot catalyst is 0.4L/m 2 (ii) a The solid content of the bimetallic ion doped carbon quantum dot catalyst aqueous solution is 27 g/L. After natural air drying, the catalyst can be directly used as a catalyst working electrode, a platinum sheet electrode is used as a counter electrode, a silver/silver chloride electrode is used as a reference electrode, and the concentration of the silver/silver chloride electrode is 1mol L –1 The cyclic voltammetry activation is carried out in the potassium hydroxide electrolyte, the scanning voltage range is 0V-1V (relative to a reversible hydrogen electrode), the scanning speed is 100mV/s, the number of scanning cycles is 10 cycles, and the iron-zinc bimetal doped carbon quantum dot electrocatalyst is obtained after activation.
Example 8
A preparation method of a bimetallic ion doped carbon quantum dot catalyst comprises the following steps: sodium citrate (0.038mol, 10g) and urea (0.049mol, 3g) were dissolved in 50ml of deionized water and added simultaneouslyCopper nitrate solution (100mg ml) –1 ) And ferric nitrate solution (100mg ml) –1 ) 0.5ml each, the molar ratio of sodium citrate to urea is 0.78:1, the molar ratio of copper nitrate to iron nitrate is 1.29: 1, the molar ratio of sodium citrate to the total amount of two different metal salts is 80: 1; stirring at room temperature for 15min to obtain a clear and transparent solution.
Transferring the mixture into a 150ml hydrothermal reaction kettle, reacting at 120 ℃ for 2h, cooling to room temperature, centrifuging the obtained black solution, and taking supernatant, namely the uniform and stable copper-iron bimetallic ion doped carbon quantum dot catalyst aqueous solution.
A preparation method of a bimetallic doped carbon quantum dot electrocatalyst comprises the following steps: directly dripping 40uL of the obtained copper-iron bimetallic ion doped carbon quantum dot catalyst aqueous solution on hydrophilic carbon paper, wherein the loading capacity of the bimetallic ion doped carbon quantum dot catalyst is 0.4L/m 2 (ii) a The solid content of the bimetallic ion doped carbon quantum dot catalyst aqueous solution is 27 g/L. After natural air drying, the catalyst can be directly used as a catalyst working electrode, a platinum sheet electrode is used as a counter electrode, a silver/silver chloride electrode is used as a reference electrode, and the concentration of the silver/silver chloride electrode is 1mol L –1 The activation is carried out in the potassium hydroxide electrolyte by cyclic voltammetry, the scanning voltage range is 0V-1V (relative to a reversible hydrogen electrode), the scanning speed is 100mV/s, the number of scanning cycles is 10 cycles, and the copper-iron bimetal doped carbon quantum dot electrocatalyst is obtained after the activation.
Example 9
A preparation method of a bimetallic ion doped carbon quantum dot catalyst comprises the following steps: sodium citrate (0.038mol, 10g) and urea (0.049mol, 3g) were dissolved in 50ml of deionized water, while copper nitrate solution (100mg ml) was added –1 ) And cobalt nitrate solution (100mg ml) –1 ) 0.5ml each, the molar ratio of sodium citrate to urea is 0.78:1, the molar ratio of copper nitrate to cobalt nitrate is 0.97: 1, the molar ratio of sodium citrate to the total amount of two different metal salts is 70: 1; stirring at room temperature for 15min to obtain a clear and transparent solution.
Transferring the mixture into a 150ml hydrothermal reaction kettle, reacting for 2 hours at 120 ℃, cooling to room temperature, centrifuging the obtained black solution, and taking supernatant fluid, namely the uniform and stable copper-cobalt bimetallic ion doped carbon quantum dot catalyst aqueous solution.
A preparation method of a bimetallic doped carbon quantum dot electrocatalyst comprises the following steps: directly dripping 40uL of the obtained copper-cobalt bimetallic ion doped carbon quantum dot catalyst aqueous solution on hydrophilic carbon paper, wherein the loading capacity of the bimetallic ion doped carbon quantum dot catalyst is 0.4L/m 2 (ii) a The solid content of the bimetallic ion doped carbon quantum dot catalyst aqueous solution is 27 g/L. After natural air drying, the catalyst can be directly used as a catalyst working electrode, a platinum sheet electrode is used as a counter electrode, a silver/silver chloride electrode is used as a reference electrode, and the concentration of the silver/silver chloride electrode is 1mol L –1 The activation is carried out in the potassium hydroxide electrolyte by cyclic voltammetry, the scanning voltage range is 0V-1V (relative to a reversible hydrogen electrode), the scanning speed is 100mV/s, the number of scanning cycles is 10 cycles, and the copper-cobalt bimetal doped carbon quantum dot electrocatalyst is obtained after the activation.
Example 10
A preparation method of a bimetallic ion doped carbon quantum dot catalyst comprises the following steps: sodium citrate (0.038mol, 10g) and urea (0.049mol, 3g) were dissolved in 50ml of deionized water, while copper nitrate solution (100mg ml) was added –1 ) And zinc nitrate solution (100mg ml) –1 ) 0.5ml each, the molar ratio of sodium citrate to urea is 0.78:1, the molar ratio of copper nitrate to zinc nitrate is 1.01: 1, the molar ratio of sodium citrate to the total amount of two different metal salts is 72: 1; stirring at room temperature for 15min to obtain a clear and transparent solution.
Transferring the mixture into a 150ml hydrothermal reaction kettle, reacting for 2 hours at 120 ℃, cooling to room temperature, centrifuging the obtained black solution, and taking supernatant fluid, namely the uniform and stable copper-zinc bimetallic ion doped carbon quantum dot catalyst aqueous solution.
A preparation method of a bimetallic doped carbon quantum dot electrocatalyst comprises the following steps: directly dripping 40uL of the obtained copper-zinc bimetallic ion doped carbon quantum dot catalyst aqueous solution on hydrophilic carbon paper, wherein the loading capacity of the bimetallic ion doped carbon quantum dot catalyst is 0.4L/m 2 (ii) a The solid content of the bimetallic ion doped carbon quantum dot catalyst aqueous solution is 27 g/L. After natural air drying, the catalyst can be directly used as a catalyst working electrode, and the platinum sheet electrodes are pairedElectrode, silver/silver chloride electrode as reference electrode, in 1mol L –1 The activation is carried out in the potassium hydroxide electrolyte by cyclic voltammetry, the scanning voltage range is 0V-1V (relative to a reversible hydrogen electrode), the scanning speed is 100mV/s, the number of scanning cycles is 10 cycles, and the copper-zinc bimetal doped carbon quantum dot electrocatalyst is obtained after the activation.
Example 11
A preparation method of a bimetallic ion doped carbon quantum dot catalyst comprises the following steps: sodium citrate (0.038mol, 10g) and urea (0.049mol, 3g) were dissolved in 50ml of deionized water, while manganese nitrate solution (100mg ml) was added -1 ) And a molybdenum nitrate solution (100mg ml) -1 ) 0.5ml each, the molar ratio of sodium citrate to urea is 0.78:1, the molar ratio of manganese nitrate to molybdenum nitrate is 1.6: 1, the molar ratio of sodium citrate to the total amount of two different metal salts is 83: 1; stirring at room temperature for 15min to obtain a clear and transparent solution.
Transferring the mixture into a 150ml hydrothermal reaction kettle, reacting for 2 hours at 120 ℃, cooling to room temperature, centrifuging the obtained black solution, and taking supernatant fluid, namely the manganese-molybdenum double-metal ion doped carbon quantum dot catalyst aqueous solution with uniform and stable shape.
A preparation method of a bimetallic doped carbon quantum dot electrocatalyst comprises the following steps: directly dripping 40uL of the obtained manganese-molybdenum double-metal ion doped carbon quantum dot catalyst aqueous solution on hydrophilic carbon paper, wherein the loading capacity of the double-metal ion doped carbon quantum dot catalyst is 0.4L/m 2 (ii) a The solid content of the bimetallic ion doped carbon quantum dot catalyst aqueous solution is 27 g/L. After natural air drying, the catalyst can be directly used as a catalyst working electrode, a platinum sheet electrode is used as a counter electrode, a silver/silver chloride electrode is used as a reference electrode, and the concentration of the silver/silver chloride electrode is 1mol L -1 The potassium hydroxide electrolyte is activated by cyclic voltammetry, the scanning voltage range is 0V-1V (relative to a reversible hydrogen electrode), the scanning speed is 100mV/s, the number of scanning cycles is 10 cycles, and the manganese-molybdenum bimetal doped carbon quantum dot electrocatalyst is obtained after activation.
Example 12
A preparation method of a bimetallic ion doped carbon quantum dot catalyst comprises the following steps: sodium citrate (0.038mol, 10g) and urea (0.049mol, 3g) were dissolved in50ml of deionized water, and a cesium nitrate solution (100mg ml) was added simultaneously -1 ) And platinum chloride solution (100mg ml) -1 ) 0.5ml each, the molar ratio of sodium citrate to urea is 0.78:1, the molar ratio of cesium nitrate to platinum chloride is 1.73: 1, the molar ratio of sodium citrate to the total amount of two different metal salts is 94: 1; stirring at room temperature for 15min to obtain a clear and transparent solution.
Transferring the cesium-platinum bimetallic ion doped carbon quantum dot catalyst into a 150ml hydrothermal reaction kettle, reacting for 2h at 120 ℃, cooling to room temperature, centrifuging the obtained black solution, and taking supernatant, namely the cesium-platinum bimetallic ion doped carbon quantum dot catalyst aqueous solution with uniform and stable shape.
A preparation method of a bimetallic doped carbon quantum dot electrocatalyst comprises the following steps: directly dripping 40uL of the obtained cesium-platinum bimetallic ion doped carbon quantum dot catalyst aqueous solution on hydrophilic carbon paper, wherein the loading capacity of the bimetallic ion doped carbon quantum dot catalyst is 0.4L/m 2 (ii) a The solid content of the bimetallic ion doped carbon quantum dot catalyst aqueous solution is 27 g/L. After natural air drying, the catalyst can be directly used as a catalyst working electrode, a platinum sheet electrode is used as a counter electrode, a silver/silver chloride electrode is used as a reference electrode, and the concentration of the silver/silver chloride electrode is 1mol L -1 The activation is carried out in the potassium hydroxide electrolyte by cyclic voltammetry, the scanning voltage range is 0V-1V (relative to a reversible hydrogen electrode), the scanning speed is 100mV/s, the number of scanning cycles is 10 cycles, and the cesium-platinum bimetallic doped carbon quantum dot electrocatalyst is obtained after the activation.
Example 13
A preparation method of a bimetallic ion doped carbon quantum dot catalyst comprises the following steps: sodium citrate (0.038mol, 10g) and urea (0.049mol, 3g) were dissolved in 50ml of deionized water, while adding a molybdenum nitrate solution (100mg ml) -1 ) And platinum chloride solution (100mg ml) -1 ) 0.5ml each, the molar ratio of sodium citrate to urea is 0.78:1, the molar ratio of the molybdenum nitrate to the platinum chloride is 1.2: 1, the molar ratio of sodium citrate to the total amount of two different metal salts is 116: 1; stirring at room temperature for 15min to obtain a clear and transparent solution.
Transferring the mixture into a 150ml hydrothermal reaction kettle, reacting for 2 hours at 120 ℃, cooling to room temperature, centrifuging the obtained black solution, and taking supernatant fluid, namely the molybdenum-platinum bimetallic ion doped carbon quantum dot catalyst aqueous solution with uniform and stable shape.
A preparation method of a bimetallic doped carbon quantum dot electrocatalyst comprises the following steps: directly dripping 40uL of the obtained molybdenum-platinum bimetallic ion doped carbon quantum dot catalyst aqueous solution on hydrophilic carbon paper, wherein the loading capacity of the bimetallic ion doped carbon quantum dot catalyst is 0.4L/m 2 (ii) a The solid content of the bimetallic ion doped carbon quantum dot catalyst aqueous solution is 27 g/L. After natural air drying, the catalyst can be directly used as a catalyst working electrode, a platinum sheet electrode is used as a counter electrode, a silver/silver chloride electrode is used as a reference electrode, and the concentration of the silver/silver chloride electrode is 1mol L -1 The activation is carried out in the potassium hydroxide electrolyte by cyclic voltammetry, the scanning voltage range is 0V-1V ((relative to a reversible hydrogen electrode), the scanning speed is 100mV/s, and the number of scanning circles is 10 circles, and the molybdenum-platinum bimetallic doped carbon quantum dot electrocatalyst is obtained after the activation.
Example 14
A preparation method of a bimetallic ion doped carbon quantum dot catalyst comprises the following steps: sodium citrate (0.038mol, 10g) and urea (0.049mol, 3g) were dissolved in 50ml of deionized water, while platinum chloride solution (100mg ml) was added -1 ) And ruthenium chloride solution (100mg ml) -1 ) 0.5ml each, the molar ratio of sodium citrate to urea is 0.78:1, the molar ratio of platinum chloride to ruthenium chloride is 0.62: 1, the molar ratio of sodium citrate to the total amount of two different metal salts is 97: 1; stirring at room temperature for 15min to obtain a clear and transparent solution.
Transferring the mixture into a 150ml hydrothermal reaction kettle, reacting for 2 hours at 120 ℃, cooling to room temperature, centrifuging the obtained black solution, and taking supernatant fluid, namely the platinum-ruthenium bimetallic ion doped carbon quantum dot catalyst aqueous solution with uniform and stable shape.
A preparation method of a bimetallic doped carbon quantum dot electrocatalyst comprises the following steps: directly dripping 40uL of the obtained aqueous solution of the platinum-ruthenium bimetallic ion doped carbon quantum dot catalyst on hydrophilic carbon paper, wherein the loading capacity of the bimetallic ion doped carbon quantum dot catalyst is 0.4L/m 2 (ii) a The solid content of the bimetallic ion doped carbon quantum dot catalyst aqueous solution is 27 g/L. Can be directly used as a catalyst working electrode after natural air drying,the platinum sheet electrode is used as a counter electrode, the silver/silver chloride electrode is used as a reference electrode, and the concentration of the silver/silver chloride electrode is 1mol L -1 The potassium hydroxide electrolyte is activated by cyclic voltammetry, the scanning voltage range is 0V-1V (relative to a reversible hydrogen electrode), the scanning speed is 100mV/s, the number of scanning cycles is 10 cycles, and the platinum-ruthenium bimetallic doped carbon quantum dot electrocatalyst is obtained after activation.
Example 15
A preparation method of a bimetallic ion doped carbon quantum dot catalyst comprises the following steps: sodium citrate (0.038mol, 10g) and urea (0.049mol, 3g) were dissolved in 50ml of deionized water, while adding a molybdenum nitrate solution (100mg ml) -1 ) And ruthenium chloride solution (100mg ml) -1 ) 0.5ml each, the molar ratio of sodium citrate to urea is 0.78:1, the molar ratio of the molybdenum nitrate to the ruthenium chloride is 0.74: 1, the molar ratio of sodium citrate to the total amount of two different metal salts is 91: 1; stirring at room temperature for 15min to obtain a clear and transparent solution.
Transferring the molybdenum-ruthenium bimetallic ion doped carbon quantum dot catalyst into a 150ml hydrothermal reaction kettle, reacting for 2h at 120 ℃, cooling to room temperature, centrifuging the obtained black solution, and taking supernatant fluid, namely the molybdenum-ruthenium bimetallic ion doped carbon quantum dot catalyst aqueous solution with uniform and stable shape.
A preparation method of a bimetallic doped carbon quantum dot electrocatalyst comprises the following steps: 40uL of the obtained molybdenum-ruthenium bimetallic ion doped carbon quantum dot catalyst aqueous solution is directly dripped on hydrophilic carbon paper, and the loading capacity of the bimetallic ion doped carbon quantum dot catalyst is 0.4L/m 2 (ii) a The solid content of the bimetallic ion doped carbon quantum dot catalyst aqueous solution is 27 g/L. After natural air drying, the catalyst can be directly used as a catalyst working electrode, a platinum sheet electrode is used as a counter electrode, a silver/silver chloride electrode is used as a reference electrode, and the concentration of the silver/silver chloride electrode is 1mol L -1 The activation is carried out in the potassium hydroxide electrolyte by cyclic voltammetry, the scanning voltage range is 0V-1V (relative to a reversible hydrogen electrode), the scanning speed is 100mV/s, the number of scanning cycles is 10 cycles, and the molybdenum-ruthenium bimetallic doped carbon quantum dot electrocatalyst is obtained after the activation.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. A preparation method of a bimetallic ion doped carbon quantum dot catalyst is characterized by comprising the following steps: the bimetallic ion doped carbon quantum dot catalyst is obtained by one step of hydrothermal reaction by using sodium citrate as a precursor carbon source, urea as a nitrogen source and metal salt as a catalytic active metal source.
2. The method for preparing the double metal ion doped carbon quantum dot catalyst according to claim 1, wherein the metal in the metal salt is selected from iron, nickel, cobalt, zinc, copper, manganese, molybdenum, cesium, platinum, ruthenium; the metal salt is selected from nitrate, chloride, sulfate and acetate of the above metals.
3. The method for preparing the bimetallic ion-doped carbon quantum dot catalyst according to claim 2, wherein the metal salt is selected from the group consisting of iron nitrate, nickel nitrate, cobalt nitrate, zinc nitrate, copper nitrate, manganese nitrate, molybdenum nitrate, cesium nitrate, platinum chloride, and ruthenium chloride.
4. The method of claim 1, wherein the method comprises the steps of:
dissolving sodium citrate and urea in a molar ratio of (0.125-8): 1 in deionized water, wherein the addition amount of the deionized water is 20-100 mL, and simultaneously adding 0.1-1 mL of each of two different metal salt solutions, wherein the concentration of the metal salt solution is 50-150 g L –1 Two kinds ofStirring for 5-20 min at room temperature to obtain clear and transparent solution, wherein the molar ratio of different metal salts is (0.25-4): 1; the molar ratio of the sodium citrate to the total amount of the two different metal salts is (20-150): 1;
and transferring the solution into a hydrothermal reaction kettle, reacting for 2-12 h at the temperature of 120-200 ℃, cooling to room temperature, centrifuging the obtained black solution, and taking supernatant to obtain the aqueous solution of the bimetallic ion doped carbon quantum dot catalyst.
5. The method for preparing the bimetallic ion-doped carbon quantum dot catalyst according to claim 4, wherein the solid content of the bimetallic ion-doped carbon quantum dot catalyst aqueous solution is 15-50 g/L.
6. A method of preparing a bimetallic doped carbon quantum dot electrocatalyst using the bimetallic ion doped carbon quantum dot catalyst prepared by the method of any one of claims 1 to 5.
7. The method according to claim 6, characterized in that it comprises the steps of:
directly coating the bimetallic ion doped carbon quantum dot catalyst aqueous solution on hydrophilic carbon paper, and directly obtaining a catalyst working electrode after natural air drying; and (2) carrying out electrochemical cyclic voltammetry in-situ activation in a potassium hydroxide solution by adopting a three-electrode system, taking a silver/silver chloride electrode as a reference electrode and a platinum sheet electrode as a counter electrode to obtain the bimetallic doped carbon quantum dot electrocatalyst.
8. The method according to claim 7, wherein the loading amount of the bimetallic ion doped carbon quantum dot catalyst is 0.1-2L/m 2 。
9. The method according to claim 7, wherein the potassium hydroxide solution has a concentration of 0.1 to 1mol L –1 The scanning voltage range of the cyclic voltammetry is 0V-1V; the scanning rate is 10-100 mV s –1 (ii) a The cycle times are 10-100 circles.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008043060A2 (en) * | 2006-10-05 | 2008-04-10 | Research Triangle Institute | Highly dispersed nickel hydrogenation catalysts and methods for making the same |
| CN106450349A (en) * | 2016-10-11 | 2017-02-22 | 北京理工大学 | Preparation method of iron-nickel hydrotalcite structure nanosheet for oxygen evolution reaction |
| CN111054343A (en) * | 2019-12-11 | 2020-04-24 | 清华-伯克利深圳学院筹备办公室 | Electrocatalytic oxygen evolution material and preparation method thereof |
| CN111229215A (en) * | 2020-03-09 | 2020-06-05 | 华东理工大学 | Metal high-dispersion supported catalyst based on carbon quantum dot induction and preparation method and application thereof |
-
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- 2022-06-24 CN CN202210722224.8A patent/CN114959770A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008043060A2 (en) * | 2006-10-05 | 2008-04-10 | Research Triangle Institute | Highly dispersed nickel hydrogenation catalysts and methods for making the same |
| CN106450349A (en) * | 2016-10-11 | 2017-02-22 | 北京理工大学 | Preparation method of iron-nickel hydrotalcite structure nanosheet for oxygen evolution reaction |
| CN111054343A (en) * | 2019-12-11 | 2020-04-24 | 清华-伯克利深圳学院筹备办公室 | Electrocatalytic oxygen evolution material and preparation method thereof |
| CN111229215A (en) * | 2020-03-09 | 2020-06-05 | 华东理工大学 | Metal high-dispersion supported catalyst based on carbon quantum dot induction and preparation method and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115944114A (en) * | 2022-12-29 | 2023-04-11 | 山东大学 | Manganese-copper double-metal doped carbon dot for removing free radicals of cigarettes |
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