CN114717597A - Molecular cage coated metal core-shell material and preparation method and application thereof - Google Patents
Molecular cage coated metal core-shell material and preparation method and application thereof Download PDFInfo
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- CN114717597A CN114717597A CN202210308113.2A CN202210308113A CN114717597A CN 114717597 A CN114717597 A CN 114717597A CN 202210308113 A CN202210308113 A CN 202210308113A CN 114717597 A CN114717597 A CN 114717597A
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- molecular cage
- hydrogen peroxide
- shell material
- coated metal
- metal
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 67
- 239000002184 metal Substances 0.000 title claims abstract description 67
- 239000002091 nanocage Substances 0.000 title claims abstract description 61
- 239000011258 core-shell material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 148
- 239000010865 sewage Substances 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 26
- 229910052799 carbon Inorganic materials 0.000 claims description 25
- 239000002243 precursor Substances 0.000 claims description 22
- 239000010411 electrocatalyst Substances 0.000 claims description 14
- 238000006722 reduction reaction Methods 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 9
- 238000011160 research Methods 0.000 abstract description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 27
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000003792 electrolyte Substances 0.000 description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 14
- 238000006555 catalytic reaction Methods 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 229910001868 water Inorganic materials 0.000 description 12
- 230000015556 catabolic process Effects 0.000 description 11
- 238000006731 degradation reaction Methods 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000003344 environmental pollutant Substances 0.000 description 9
- 231100000719 pollutant Toxicity 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000011780 sodium chloride Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 229910021607 Silver chloride Inorganic materials 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 6
- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical compound Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 6
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 5
- 238000006213 oxygenation reaction Methods 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910000348 titanium sulfate Inorganic materials 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- 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 4
- 239000003960 organic solvent Substances 0.000 description 4
- 101000668416 Homo sapiens Regulator of chromosome condensation Proteins 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 102100039977 Regulator of chromosome condensation Human genes 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000000970 chrono-amperometry Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 2
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 235000006694 eating habits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- -1 sulfate radical Chemical class 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/28—Per-compounds
- C25B1/30—Peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a molecular cage coated metal core-shell material and a preparation method and application thereof. The invention applies high-concentration hydrogen peroxide prepared by electrocatalysis to the sewage treatment neighborhood for the first time in situ, and is a research for directly treating sewage in situ based on hydrogen peroxide prepared by pulse electrocatalysis.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis pulse and in-situ water body treatment, and particularly relates to a molecular cage coated metal core-shell material, a preparation method thereof, hydrogen peroxide preparation and water treatment application.
Background
With the highly developed industrial age, the existence of three major problems of resource shortage, environmental pollution, ecological destruction and the like caused by various international sanitary events frequently seriously threatens the survival of human beings. At present, environmental pollution has been known as a global concern. Causing various serious water body pollution, ocean pollution and the like. The ecological balance of the earth and the clothes and eating habits of people are seriously damaged by the characteristics of burst property, large area, long duration, serious damage and the like. Therefore, the sewage problem has become a target of all-human co-efforts and urgent solutions. Active metal is usually selected as a reaction for preparing hydrogen peroxide by catalyzing oxygen reduction, four-electron reaction easily occurs due to overhigh activity, water is usually directly generated, inert metal is adopted as an electrocatalyst for preparing hydrogen peroxide in the prior art, and the catalytic reaction is difficult to realize due to low catalytic efficiency caused by poor activity; some carbon-based materials tend to increase catalyst instability and preparation complexity due to insufficient activity and loading and handling.
Disclosure of Invention
The invention discloses a method for preparing high-concentration hydrogen peroxide by an electric pulse method, and the prepared hydrogen peroxide is directly applied to sewage treatment, so that the problem of incomplete sewage treatment caused by insufficient oxidation of the hydrogen peroxide is solved. Because the commercial power catalyzes the preparation of the hydrogen peroxide, the hydrogen peroxide can be prepared on site only by water and electricity, and the problem that the hydrogen peroxide is not safe for transportation is solved; and the hydrogen peroxide has the advantages of no secondary pollution, environmental protection and safety because only water and oxygen or hydrogen are produced. The research lays a foundation for the practical application of preparing high-concentration hydrogen peroxide and treating sewage in situ in the future.
The invention adopts the following technical scheme:
a metal core-shell material coated by a molecular cage comprises a metal and the molecular cage, wherein the metal is positioned in the molecular cage; the molecular weight of the molecular cage is 800-1500; the metal includes a transition metal, preferably a transition metal of the first series.
The porous carbon sphere coated metal catalyst is obtained by calcining the molecular cage coated metal core-shell material.
Mixing a molecular cage precursor and a metal precursor, and then carrying out reduction reaction to obtain a molecular cage coated metal core-shell material; and calcining the molecular cage coated metal core-shell material to obtain the porous carbon sphere coated metal catalyst. Preferably, the molecular cage precursor and the metal precursor are mixed in a solvent for 0.1-1 day, then a reducing substance is added for reduction reaction for 1-5 hours to obtain a molecular cage coated metal core-shell material, and further, after the reduction reaction is finished, centrifugal washing and drying are carried out to obtain the molecular cage coated metal core-shell material; the solvent is chloroform, dichloromethane, methanol, etc. And calcining the molecular cage coated metal core-shell material at the temperature of 400-550 ℃ for 2-5 hours to obtain the heteroatom-doped porous carbon sphere coated metal catalyst.
In the invention, the molecular cage precursor contains carbon-nitrogen double bonds and is reduced into carbon-nitrogen single bonds to obtain reduced molecular cages; preferably, the chemical structural formula of the molecular cage precursor of the present invention is as follows:
the chemical structural formula of the molecular cage is as follows:
the metal precursor is a metal salt, typically a water-soluble inorganic metal salt, such as ferric nitrate, ferric sulfate, ferric chloride, zinc nitrate, nickel nitrate, and the like.
The porous carbon sphere coated metal catalyst is obtained by the steps of preparing a molecular cage precursor, adsorbing metal, reducing a molecular cage precursor metal coating and calcining the molecular cage metal coating at high temperature in sequence. In the invention, trimesic aldehyde and cyclohexanediamine are used for preparing a molecular cage precursor under the catalysis of trifluoroacetic acid; the molar ratio of the trimesic aldehyde to the cyclohexanediamine to the trifluoroacetic acid is 1: 1.5-2: 0.3-0.7. As an example, the molecular cage precursor is prepared by mixing 1, 2-cyclohexanediamine and benzene-1, 3, 5-trimethylaldehyde (trimesic-trimethylaldehyde) in an organic solvent, dropping trifluoroacetic acid with stirring, covering, and reacting with stirring at room temperature to form a molecular cage; subsequently, washing with a washing solvent, filtration and drying were carried out to obtain CC1 molecular cages. The organic solvent is chloroform, dichloromethane and other organic solvents, and the reaction time is 1-4 days; after the reaction is finished, the washing solvent is acetone, dichloromethane, alcohol, ethyl acetate and the like, and the washing times are 3-8.
According to the invention, the molecular cage precursor is subjected to reduction reaction after adsorbing the metal precursor to obtain the molecular cage coated metal core-shell material. As an example, a molecular cage precursor and a metal precursor are added into an organic solvent such as chloroform, dichloromethane and methanol, and the adsorption time is 0.1-1 day; after adsorption, adding reducing substances for reaction for 1-5 h; centrifuging and washing the sample by using a solvent, wherein the centrifugal solvent is dichloromethane, alcohol, ethyl acetate, water and the like, the washing solvent is dichloromethane, alcohol, ethyl acetate and the like, and the washing times are 3-8; and drying the sample after washing, wherein the drying temperature is 60-110 ℃, and the drying time is 6-24 hours. Metal precursors such as: ferric nitrate, ferric sulfate, ferric chloride, zinc nitrate, nickel nitrate, and the like. After drying, the product is treated in a tube furnace at 400-550 ℃ for 3-4 hours, and finally the porous carbon sphere coated metal catalyst doped with the heteroatom is obtained.
The invention discloses an application of the molecular cage coated metal core-shell material or the porous carbon sphere coated metal catalyst in preparation of hydrogen peroxide and/or sewage treatment, and particularly relates to an electrocatalyst prepared by coating metal on porous carbon spheres.
The invention discloses a method for preparing hydrogen peroxide, which takes a porous carbon sphere coated metal catalyst as an electrocatalyst to prepare the hydrogen peroxide in an H-shaped electrolytic cell, preferably by pulse electrocatalysis.
The invention discloses a sewage treatment method, which uses the porous carbon ball coated metal catalyst as an electrocatalyst to carry out sewage treatment in an H-shaped electrolytic cell, preferably pulse electrocatalysis.
The porous carbon sphere coated metal catalyst is used as an electrocatalyst for preparing hydrogen peroxide by pulse electro-catalysis or treating organic pollutant sewage while preparing the hydrogen peroxide by pulse electro-catalysis. Specifically, the electrocatalyst is uniformly mixed with carbon powder, adhesive and solvent, and directly drop-coated on the surface of carbon paper, carbon cloth or carbon felt as working electrode, preferably on the working electrode, and the density of the electrocatalyst is 0.03-0.1mg/cm2. An electrocatalyst,The dosage ratio of the carbon powder, the adhesive and the solvent is (1-5 mg): (10-20 muL): (300-.
When the hydrogen peroxide is prepared by pulse electro-catalysis or the hydrogen peroxide is prepared by pulse electro-catalysis and organic pollutant sewage is treated, the pulse voltage is 0.3-1V (Vs RHE), the pulse width is 0.1-100 s, the pulse gap is 0.1-100 s, and the electro-catalysis time is 2-50 h.
The invention realizes the function of treating sewage while preparing hydrogen peroxide by electrocatalysis, and directly adds ions which often exist in water body while preparing hydrogen peroxide by treating sewage/electric pulse, checks whether the ions affect the preparation of the hydrogen peroxide, and samples at different time periods to detect whether pollutants are thoroughly degraded. Specifically, ions frequently existing in the water body comprise calcium, magnesium, sodium, potassium, sulfate radical, nitrate radical, chloride ions and the like, and the addition amount is 5-100 ppm, so that the preparation of the hydrogen peroxide is not influenced. The hydrogen peroxide can degrade organic pollutants in the sewage in situ.
The hydrogen peroxide prepared by electrocatalysis of the invention is an excellent and proper green solution, can eliminate harmful bacteria, organic molecules, taste and smell, and does not leave any residue. Superoxide hydroxyl radicals and hydroxyl radicals are considered highly reactive media for water treatment, and hydroxyl radicals have a short lifetime (nanoseconds) in aqueous media and are therefore automatically removed from the treatment system. The electrocatalyst with weak hydroxyl radical free energy has high selectivity to double electron paths. The strong hydroxyl radical free energy should be strong enough to dissociate the water molecules and provide a good thermodynamic driving force for the two electron pathway to generate hydrogen peroxide. The invention provides the method for preparing hydrogen peroxide and directly applying the hydrogen peroxide to sewage treatment, thereby realizing the direct application of hydroxyl radicals and superoxide hydroxyl radicals in sewage treatment.
The invention selects simple molecular cage coated transition metal, not only can realize two-electron reaction of high-stability catalytic oxygen reduction, but also increases the utilization efficiency and high selectivity of the catalyst. The method has universality, and can coat and coordinate various metals to realize the reaction of preparing the hydrogen peroxide by catalyzing the various metals with high stability and high selectivity. The preparation of high-concentration hydrogen peroxide is realized by an electric pulse technology and is directly applied to sewage treatment. Reports related to the application of the molecular cage coated metal core-shell material in preparing hydrogen peroxide by pulse electro-catalysis and directly treating sewage in situ are not seen so far.
Compared with the prior art, the invention has the following advantages:
(1) the molecular cage coated metal particle material prepared by the invention is used as an electrocatalyst material to prepare hydrogen peroxide, and has high selectivity and yield; the preparation of high concentrations of hydrogen peroxide was successfully achieved by a pulse process.
(2) Compared with the traditional device, the device realizes the functions of hydrogen peroxide preparation and sewage treatment, has great application value in hydrogen peroxide preparation research, and the prepared high-concentration hydrogen peroxide has direct practical value, and the prepared hydrogen peroxide in-situ sewage treatment is realized by directly applying the hydrogen peroxide, so that the device has great significance in scientific research and practical application.
Drawings
Fig. 1 is a judgment on the yield of hydrogen peroxide.
Fig. 2 is a characterization of the composite material.
FIG. 3 shows the results of electrocatalytic production of hydrogen peroxide.
FIG. 4 shows the current efficiency measurements of three catalysts in 0.1mol/L different electrolytes (sodium sulfate, potassium hydroxide, sodium chloride).
Fig. 5 shows the results of the degradation of the contaminants.
Detailed Description
The raw materials of the invention are all the existing products, the specific preparation method and the test method are conventional technologies, and if no special description is provided, the operation is carried out at room temperature and in the air. KOH aqueous solution, NaCl aqueous solution or Na2SO4The aqueous solution was used as electrolyte, the rotating ring-disk electrode (RRDE) measurements were performed in a typical three-electrode H cell at 25 deg.C, platinum foil (99.99%, Beantown Chemical) was used as counter electrode, and saturated calomel electrode (SCE, CH instrument) or Ag/AgCl was used as reference electrode. RRDE is powered by AFE7R9GCPT (Pine Instruments) glassy carbon rotating diskA pole (Φ =5.0 mm) and a Pt ring (Φ =15.0 mm) were assembled with a theoretical collection efficiency of 27%.
The yield judgment of hydrogen peroxide by the cerium amount method and the titanium sulfate method is compared, as shown in fig. 1. Preparing a cerium sulfate solution with a certain concentration by using a 0.5 mol/L sulfuric acid solution, detecting ultraviolet absorption spectrums with different concentrations by using an ultraviolet absorption spectrum as shown in (a) of figure 1, collecting an absorbance value with the wavelength of 317nm as a standard curve as shown in (b) of figure 1 to obtain a linear fitting equation and a polynomial fitting equation, and reversely deducing the comparison between the concentration of the hydrogen peroxide and the actual concentration by using the fitting equation as shown in (c) of figure 1. Preparing a titanium sulfate solution with a certain concentration by using a 0.5 mol/L sulfuric acid solution, detecting ultraviolet absorption spectra with different concentrations by using an ultraviolet absorption spectrum as shown in (d) of fig. 1, collecting an absorbance value with a wavelength of 410 nanometers as a standard curve as shown in (e) of fig. 1 to obtain a linear fitting equation and a polynomial fitting equation, and reversely deducing the comparison between the concentration of the hydrogen peroxide and the actual concentration by using the fitting equation as shown in (f) of fig. 1. The calculated concentration is closer to the actual concentration. From (c) and (f) in fig. 1, it can be seen that the detection of hydrogen peroxide concentration by titanium sulfate is more accurate than the method of cerium sulfate, and the polynomial processing method is more accurate than the linear processing method. The amount of hydrogen peroxide was determined by the titanium sulfate method.
Example one
1, 2-cyclohexanediamine (61.95. mu.L, 1.085 mmol) and benzene-1, 3, 5-trimethylaldehyde (50 mg, 0.62 mmol) were dissolved in 5mL of dichloromethane, respectively, and then mixed, followed by dropwise addition of 5mL of dichloromethane containing trifluoroacetic acid (26.2. mu.L, 0.27 mmol) with stirring; then, the reaction was stirred at room temperature for 36 hours, followed by washing with ethyl acetate, ethanol and dichloromethane, filtration and drying at 60 ℃ to obtain a molecular cage precursor (CC 1).
Dissolving 111.7mg of CC1 and 113.4mg of zinc nitrate in 10mL of chloroform/methanol (volume ratio 1/1) mixed solution, stirring at room temperature for 12 hours, adding 0.05mg of PVP (polyvinylpyrrolidone) dispersing agent and 100mg of sodium borohydride reducing agent, stirring for 2 hours, centrifuging the mixture at 6000 rpm for 5 minutes, washing with ultrapure water, ethanol and ethyl acetate for three times, and drying to obtain the molecular cage coated metal core-shell material; then the molecular cage coated metal core-shell material is treated in a 500 ℃ tube furnace for 4 hours (air, 10 ℃/min), and finally the porous carbon sphere coated metal catalyst doped with the heteroatom is obtained and used as the catalyst of the following experiment. The metal salts are respectively zinc chloride, ferric chloride and nickel nitrate, and correspond to Zn/RCC1, Fe/RCC1 and Ni/RCC 1.
The successful synthesis and reduction of the molecular cage are proved by (a) in fig. 2 and (b) in fig. 2 for detecting the molecular weight of the molecular cage precursor and the molecular weight of the reduced molecular cage by matrix-assisted laser desorption ionization time-of-flight mass spectrometry. Powder x-ray diffraction detection of the synthesized molecular cage is shown in (c) in fig. 2 and detection of the reduced molecular cage crystal is shown in (d) in fig. 2, nuclear magnetic data of detection of the molecular cage coated metal core-shell material is shown in (e) in fig. 2, and no nuclear magnetic peak is generated, so that the successful coating of the nickel, iron and zinc by the reduced molecular cage is proved.
Example two
0.1 mol/LKOH aqueous solution, NaCl aqueous solution or Na2SO4The aqueous solution is used as electrolyte. The rotating ring-disk electrode (RRDE) measurements were performed in a typical three-electrode H cell at 25 ℃. Platinum foil (99.99%, Beantown Chemical) was used as the counter electrode and a saturated calomel electrode (SCE, CH instrument) or Ag/AgCl was used as the reference electrode. RRDE is assembled from AFE7R9GCPT (Pine Instruments) glassy carbon rotating disk electrode (Φ =5.0 mm) and Pt ring (Φ =15.0 mm) with a theoretical collection efficiency of 27%.
A process for the long-term production of hydrogen peroxide in an H-type electrolytic cell.
The catalyst paste is formed by ultrasonic mixing of 485 muL of methanol, 15 muL of Nafion, 2.5 mg of carbon powder and 2.5 mg of catalyst, and 60 muL of catalyst paste is dropwise coated on carbon paper (2 cmx2 cm) to serve as a working electrode. Platinum foil (99.99%, Beantown Chemical) was used as the counter electrode and Ag/AgCl was used as the reference electrode. Under the constant potential polarization of 0.6 vs RHE or the voltage application of 0.6 vs RHE, the current is measured for 0.1s, and the hydrogen peroxide is prepared by electro-catalysis. The voltage of the pulse was 0.6V (Vs RHE), the pulse width was 0.1s, and the pulse gap was 0.1 s.
FIG. 3 shows the results of electrocatalytic production of hydrogen peroxide. The platinum wire is used as a counter electrode, and the silver/silver chloride is used as a reference electrode. Fig. 3 (a) shows that, when the zinc molecular cage catalyst (Zn/RCC 1) and the potassium hydroxide aqueous solution are used as the electrolyte, and the constant potential mode (CP) and the pulse potential (CA) are scanned for a certain period of time, the yield of the hydrogen peroxide detected by the constant potential is about 3 mmol/l, the concentration cannot be increased any more, and the yield of the hydrogen peroxide detected by the pulse potential can finally reach about 80 mmol/l. In fig. 3 (b) it is shown that hydrogen peroxide is produced in electrolytes of sodium chloride, sodium sulphate and potassium hydroxide by comparison of Constant Potential (CP) and pulsed potential Cyclic Voltammetry (CV) and pulsed potential (CA), respectively, which results in a maximum concentration of about 170 mmol/l of hydrogen peroxide produced by pulsed potential catalysis in sodium chloride electrolyte, which is the maximum to select a suitable electrolyte for subsequent contaminant degradation. In the potassium hydroxide electrolyte, the maximum current efficiency of two electrodes, the rotating ring disk electrode and the carbon paper surface on which three catalysts are dripped, is measured as shown in fig. 3 (c). The maximum hydrogen peroxide yield which can be finally achieved is detected by respectively detecting two electrochemical catalysis methods of constant potential and pulse potential of three catalysts which are dripped on the surface of the carbon paper in potassium hydroxide electrolyte, and the graph is shown in figure 3 (d), and figure 4 is the current efficiency detection of the three catalysts in different electrolytes (sodium sulfate, potassium hydroxide and sodium chloride) of 0.1 mol/L. The three catalysts can be used for preparing hydrogen peroxide, the concentration of pulse preparation is far greater than that of constant potential catalysis, and the molecular cage coordination metal and pulse potential catalysis modes are proved to have universality.
EXAMPLE III
The catalyst paste is formed by ultrasonically mixing 485 mu L of methanol, 15 mu L of Nafion, 2.5 mg of carbon powder and 2.5 mg of catalyst Zn/RCC1, 60 mu L of catalyst paste is taken and dropwise coated on carbon paper (2 cmx2 cm) to serve as a working electrode, a pollutant rhodamine 6G is dissolved in 100 ml of 0.1mol/L NaCl aqueous solution (20 mg/L) to serve as electrolyte, a platinum foil (99.99%, Beantown Chemical) serves as a counter electrode, and Ag/AgCl serves as a reference electrode. Under the condition of oxygenation or no oxygenation, pollutants are catalytically degraded by a chronoamperometry, the concentration of the pollutants is directly detected by ultraviolet, the concentration of hydrogen peroxide is detected by a cerium sulfate method, and the pollutants are degraded in situ in the process of preparing the hydrogen peroxide by electrocatalysis under the condition of oxygenation. The voltage of the pulse was 0.6V (Vs RHE), the pulse width was 0.1s, and the pulse gap was 0.1 s.
Fig. 5 shows the results of the degradation of the contaminants. Rhodamine 6G was chosen as the pollutant for electrocatalytic degradation to demonstrate that the generation of hydrogen peroxide is thorough for the degradation of organic matter and can accelerate the degradation. The platinum wire is used as a counter electrode, the silver/silver chloride is used as a reference electrode, and the working electrode is prepared by mixing zinc, powder sintered by a molecular cage and carbon powder and dripping the mixture on carbon paper. A rhodamine 6G solution with a certain concentration is prepared in water, ultraviolet absorption spectra with different concentrations are detected by ultraviolet absorption spectra and are shown in (a) in figure 5, and the absorbance value with the wavelength of 528 nanometers is collected and is used as a standard curve and is shown in (b) in figure 5. Under the condition of oxygenation or no oxygenation, pollutants are catalytically degraded by a chronoamperometry, 20 millimole/liter of rhodamine 6G is directly added into the two electrolytic cells respectively, electrocatalysis is started by pulse potential, the residual concentration of the rhodamine is monitored by ultraviolet light after a certain time, oxygen is not introduced into the electrolyte to serve as a comparison experiment, the degradation result is shown in a figure 5 (c), and the degradation result of the oxygen introduced into the electrolyte is shown in a figure 5 (d). The result shows that about 200 minutes is needed for degrading rhodamine 6G completely by continuously introducing oxygen into the electrolytic cell, while 10 hours is needed for degrading without introducing oxygen into the electrolyte or the degradation is incomplete, and 1.9 millimole/liter of rhodamine 6G remains; the introduction of oxygen is illustrated as the preparation of hydrogen peroxide and the removal of contaminants.
Hydrogen peroxide plays an important role in chemical industries such as paper making, electronics, industrial wastewater treatment, oxidation and the like, and the hydrogen peroxide is always a key problem which hinders the development and application of the hydrogen peroxide in the field of sewage treatment because of insufficient sewage treatment capacity and transportation safety. The invention selects the titanium sulfate method, and the polynomial detection of the concentration of the hydrogen peroxide has high accuracy. The prepared molecular cage coated metal particle material is used as an electrocatalyst, a molecular cage ligand is suitable for coordination of various metal ions to prepare hydrogen peroxide, and the molecular cage ligand has universality. The yield of hydrogen peroxide prepared by different electrolytes and different catalysts in three modes of a potentiostatic method, cyclic voltammetry and pulse electrocatalysis is proved to have universality for improving the yield of hydrogen peroxide prepared by a pulse method. The pulse electrochemical method for preparing high-concentration hydrogen peroxide can be directly used for in-situ degradation of pollutants. Compared with the traditional catalyst, preparation method and pollutant degradation method, the method provided by the invention has the advantages that the function of sewage treatment is directly realized while hydrogen peroxide is prepared, the preparation and research of hydrogen peroxide have very high application value, the prepared high-concentration hydrogen peroxide has direct practical value, the prepared hydrogen peroxide is directly applied to sewage treatment, and the method has great significance in scientific research and practical application.
Claims (10)
1. A metal core-shell material coated by a molecular cage comprises a metal and the molecular cage, and is characterized in that the metal is positioned in the molecular cage; the molecular weight of the molecular cage is 800-1500.
2. The molecular cage coated metallic core-shell material of claim 1, wherein the metal comprises a transition metal.
3. The method for preparing a metal core-shell material coated with a molecular cage according to claim 1, wherein the metal core-shell material coated with a molecular cage is obtained by mixing a molecular cage precursor with a metal precursor and then performing a reduction reaction.
4. The method for preparing a molecular cage coated metal core-shell material according to claim 3, wherein the molecular cage precursor contains carbon-nitrogen double bonds; the metal precursor is a metal salt.
5. A porous carbon sphere coated metal catalyst, which is characterized by being obtained by calcining the molecular cage coated metal core-shell material as claimed in claim 1.
6. The method for preparing the porous carbon sphere-coated metal catalyst according to claim 5, wherein the porous carbon sphere-coated metal catalyst is obtained by calcining the molecular cage-coated metal core-shell material according to claim 1.
7. Use of the molecular cage coated metal core-shell material of claim 1 or the porous carbon sphere coated metal catalyst of claim 5 in the preparation of hydrogen peroxide and/or in sewage treatment.
8. Use according to claim 7, wherein the catalyst is an electrocatalyst.
9. A method for preparing hydrogen peroxide, characterized in that the hydrogen peroxide is prepared in an H-type electrolytic cell by using the porous carbon sphere-coated metal catalyst of claim 5 as an electrocatalyst.
10. A sewage treatment method, characterized in that the porous carbon sphere-coated metal catalyst of claim 5 is used as an electrocatalyst, and sewage treatment is carried out in an H-type electrolytic cell.
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| CN109192990A (en) * | 2018-08-10 | 2019-01-11 | 成都新柯力化工科技有限公司 | A kind of class molecule cage clad alloy catalyst and preparation method for fuel cell |
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