CN115215411A - MOF-Ti doped with rare earth metal 4 O 7 Preparation method of composite electrode - Google Patents
MOF-Ti doped with rare earth metal 4 O 7 Preparation method of composite electrode Download PDFInfo
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- CN115215411A CN115215411A CN202210939905.XA CN202210939905A CN115215411A CN 115215411 A CN115215411 A CN 115215411A CN 202210939905 A CN202210939905 A CN 202210939905A CN 115215411 A CN115215411 A CN 115215411A
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 56
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 238000005245 sintering Methods 0.000 claims abstract description 55
- 239000000843 powder Substances 0.000 claims abstract description 51
- 238000003756 stirring Methods 0.000 claims abstract description 36
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000002490 spark plasma sintering Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 19
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 239000012752 auxiliary agent Substances 0.000 claims description 12
- 239000011812 mixed powder Substances 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 229910052771 Terbium Inorganic materials 0.000 claims description 6
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 6
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 5
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 5
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052772 Samarium Inorganic materials 0.000 claims description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 5
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 5
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 5
- 229940014800 succinic anhydride Drugs 0.000 claims description 5
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052773 Promethium Inorganic materials 0.000 claims description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 7
- 238000012546 transfer Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 12
- -1 rare earth ions Chemical class 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- CDOWNLMZVKJRSC-UHFFFAOYSA-N 2-hydroxyterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(O)=C1 CDOWNLMZVKJRSC-UHFFFAOYSA-N 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- CJIJXIFQYOPWTF-UHFFFAOYSA-N 7-hydroxycoumarin Natural products O1C(=O)C=CC2=CC(O)=CC=C21 CJIJXIFQYOPWTF-UHFFFAOYSA-N 0.000 description 3
- 229960000956 coumarin Drugs 0.000 description 3
- 235000001671 coumarin Nutrition 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- ORHBXUUXSCNDEV-UHFFFAOYSA-N umbelliferone Chemical compound C1=CC(=O)OC2=CC(O)=CC=C21 ORHBXUUXSCNDEV-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 2
- PMOWTIHVNWZYFI-UHFFFAOYSA-N o-Coumaric acid Natural products OC(=O)C=CC1=CC=CC=C1O PMOWTIHVNWZYFI-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000003115 supporting electrolyte Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000149 chemical water pollutant Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- HDCOFJGRHQAIPE-UHFFFAOYSA-N samarium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HDCOFJGRHQAIPE-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- UTCARTSNNKGRTD-UHFFFAOYSA-N terbium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Tb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O UTCARTSNNKGRTD-UHFFFAOYSA-N 0.000 description 1
- KPZSTOVTJYRDIO-UHFFFAOYSA-K trichlorocerium;heptahydrate Chemical compound O.O.O.O.O.O.O.Cl[Ce](Cl)Cl KPZSTOVTJYRDIO-UHFFFAOYSA-K 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- QBAZWXKSCUESGU-UHFFFAOYSA-N yttrium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QBAZWXKSCUESGU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- 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
Abstract
The invention discloses a rare earth metal doped MOF-Ti 4 O 7 A method for preparing a composite electrode. The electrode is made of Ti 4 O 7 The powder and the rare earth MOFs are prepared by ultrasonic mixing, heating and stirring, drying and adopting a spark plasma sintering technology. The rare earth metal doped MOF-Ti of the invention 4 O 7 Rare earth MOFs introduced in the preparation method of the composite electrode can realize rare earth metal doping in the electrode sintering process, the interface charge transfer rate of the prepared composite electrode is obviously enhanced, the OH production capacity is greatly improved, and the preparation method is obviously superior to that of Ti doped with pure rare earth metal 4 O 7 Electrode, greatly improves Ti 4 O 7 The electrocatalytic reaction activity of the electrode has higher sewage treatment efficiency.
Description
Technical Field
The invention relates to the technical field of electrochemistry, in particular to a rare earth metal dopedHeteromof-Ti 4 O 7 A method for preparing a composite electrode.
Background
In recent years, advanced oxidation technology has wide application and remarkable advantages in the aspect of advanced treatment of coking wastewater, landfill leachate and the like, wherein the electrochemical oxidation technology is distinguished from the advantages of no need of medicament addition, environmental protection, simple and convenient operation, high treatment energy efficiency and the like. Ti 4 O 7 The material is a brand-new energy-saving, high-efficiency and environment-friendly electrode material, has high acid and alkali corrosion resistance, wear resistance, good stability and durability, high conductivity, chemical stability, wide potential window and the like. Ti 4 O 7 The anode can degrade pollutants through direct electron transfer, and can also remove pollutants through indirect oxidation by generating hydroxyl radicals, so that the anode is an ideal electrode material for sewage treatment. But Ti 4 O 7 As an anode material, the problems of low yield of hydroxyl radicals and low charge transfer rate still exist, so that the further popularization and application of the material are limited. Therefore, there is an urgent need to develop a method for significantly improving Ti 4 O 7 A method for preparing an anode catalytic active electrode.
Rare earth MOFs have attracted considerable attention in recent years due to their fluorescent, magnetic, and sensing properties. The rare earth ions have a 4f electron layer structure with high coordination number, high charge and incomplete filling, so that oxygen supply ligands or nitrogen supply ligands such as carboxylic acid organic ligands can be combined more easily, and due to the synergistic effect of the rare earth ions and the ligands, various rare earth MOFs materials with good performance and various structures can be synthesized. Therefore, it is expected to mix the rare earth MOFs with Ti 4 O 7 Combining to prepare the rare earth metal doped MOF-Ti 4 O 7 And (3) a composite electrode.
Disclosure of Invention
The invention aims to provide a rare earth metal doped MOF-Ti 4 O 7 A method for preparing a composite electrode, which aims to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
MOF-Ti doped with rare earth metal 4 O 7 The preparation method of the composite electrode comprises the following steps:
taking diatomite and an auxiliary agent, stirring uniformly, and adding Ti 4 O 7 The powder, the rare earth MOFs powder and the acetone solution are uniformly mixed by ultrasonic, heated and stirred, and dried in vacuum to obtain mixed powder, high-temperature sintering is carried out by utilizing a spark plasma sintering technology, the temperature rise rate of the spark plasma sintering is 50-60 ℃/min, the sintering temperature is 1000-1100 ℃, the sintering time is 20-30min, and the sintering pressure is 2-4MPa, so that the electrode is prepared.
Preferably, the rare earth metal in the rare earth MOFs powder is any one or more of lanthanum, cerium, praseodymium, terbium, yttrium, neodymium, promethium, samarium, europium and gadolinium.
Preferably, the Ti 4 O 7 The powder has a diameter of 100nm-1 μm.
Preferably, the mixed powder comprises the following components: 0.4-0.8 part of diatomite, 2-3.5 parts of auxiliary agent and 0.8-1.5 parts of Ti 4 O 7 Powder, 0.8-1.5 parts of rare earth MOFs powder.
Preferably, the ultrasonic mixing time is 30-90min.
Preferably, the heating and stirring speed is 150-180r/min, and the heating temperature is 60-80 ℃.
Preferably, the vacuum drying temperature is 70-90 ℃, and the drying time is 10-24h.
Preferably, the preparation method of the auxiliary agent comprises the following steps: adding sodium dodecyl benzene sulfonate, hexadecyl trimethyl ammonium bromide and deionized water into modified polyvinyl alcohol, stirring uniformly, adding butyraldehyde and hydrochloric acid, cooling to 8-10 ℃, reacting for 1-1.5h, and adjusting the pH to 8-9 after the reaction is finished to obtain the assistant.
Preferably, the preparation method of the modified polyvinyl alcohol comprises the following steps: uniformly stirring polyvinyl alcohol and dimethyl sulfoxide at 50-55 ℃, adding triethylamine and succinic anhydride, reacting for 1.5-2.5h, adding N-hydroxysuccinimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, reacting for 20-40min, adding an amino-terminated branched polymer, and stirring for 22-26h to obtain the modified polyvinyl alcohol.
Preferably, the preparation method of the amino-terminated branched polymer comprises the following steps: taking diethylenetriamine, N-methylene bisacrylamide and N, N-dimethylformamide to react for 22-24h at the temperature of 60-70 ℃ to obtain the amino-terminated branched polymer.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention is realized by adding Ti 4 O 7 Rare earth MOFs crystal materials are introduced in the electrode preparation process, and carbon/rare earth metal oxides are formed in the plasma sintering process, so that rare earth metal doping can be realized in one step, the conductivity is improved, the interface charge transfer rate is favorably enhanced, and the catalytic activity and the stability of the electrode are improved.
(2) The invention adds diatomite which has large specific surface area and is loaded with Ti 4 O 7 Powder and rare earth MOF powder capable of preventing Ti 4 O 7 Agglomeration of the powder and rare earth MOF powder. Adding modified polyvinyl alcohol, the amino group on the modified polyvinyl alcohol can react with the silicon hydroxyl group on the diatomite to make Ti loaded 4 O 7 The diatomite of the powder and the rare earth MOF powder is dispersed more uniformly in the system, and the Ti is improved 4 O 7 Catalytic activity, stability and the ability to degrade contaminants of the electrode.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
MOF-Ti doped with rare earth metal 4 O 7 The preparation method of the composite electrode comprises the following specific steps:
taking 0.8g of Ti with the diameter of 100nm 4 O 7 Powder and 0.8g of terbium-based MUltrasonically mixing OF powder in 50mL OF acetone solution for 30min, heating and stirring to be nearly dry at the stirring speed OF 150r/min, heating to 60 ℃, and drying in vacuum at 70 ℃ for 10h to obtain mixed powder; sintering at high temperature and high pressure by adopting spark plasma sintering, wherein the heating rate is 50 ℃/min, the sintering pressure is 2MPa, the sintering temperature is 1000 ℃, and the sintering time is 20min, so as to prepare the electrode.
Ti of 100nm diameter 4 O 7 The powder was purchased from beijing lihebo new materials ltd.
The preparation method of the terbium-based MOF powder comprises the steps of adding 0.91g of terbium nitrate hexahydrate and 0.64g of 2, 5-furandicarboxylic acid into a polytetrafluoroethylene reaction kettle containing a 50mLN and N-dimethylformamide solvent, carrying out ultrasonic oscillation for 30min, then placing the reaction kettle into a constant-temperature drying oven, preserving heat for 24h at 120 ℃, naturally cooling to room temperature after the reaction is finished, respectively washing 3 times by using N, N-dimethylformamide and ethanol, and then carrying out vacuum drying for 12h at 90 ℃, thus obtaining the terbium-based MOF powder.
Example 2
MOF-Ti doped with rare earth metal 4 O 7 The composite electrode comprises the following specific steps:
1.0g of Ti having a diameter of 0.5 μm was taken 4 O 7 Ultrasonically mixing the powder and 1.0g of yttrium-based MOF powder in 80mL of acetone solution for 60min, heating and stirring to be nearly dry at the stirring speed of 170r/min, heating to 70 ℃, and drying in vacuum at 80 ℃ for 18h to obtain mixed powder; sintering at high temperature and high pressure by adopting spark plasma sintering, wherein the sintering process comprises the following steps: the sintering temperature rise rate is 60 ℃/min, the sintering pressure is 3MPa, the sintering temperature is 1100 ℃, and the sintering time is 30min, so that the electrode is prepared.
Ti of 0.5 μm diameter 4 O 7 The powder was purchased from new materials, inc. of Lihebo, beijing.
The preparation method of the yttrium-based MOF powder comprises the steps of adding 0.77g of yttrium nitrate hexahydrate and 0.64g of 2, 5-furandicarboxylic acid into a polytetrafluoroethylene reaction kettle containing a 50mLN and N-dimethylformamide solvent, carrying out ultrasonic oscillation for 30min, placing the reaction kettle into a constant-temperature drying oven, preserving heat for 24h at 120 ℃, naturally cooling to room temperature after the reaction is finished, washing for 3 times by using N, N-dimethylformamide and ethanol in sequence, and then carrying out vacuum drying for 12h at 90 ℃ to obtain the yttrium-based MOF powder.
Example 3
MOF-Ti doped with rare earth metal 4 O 7 The preparation method of the composite electrode comprises the following specific steps:
1.5g of Ti having a diameter of 1 μm were taken 4 O 7 Ultrasonically mixing the powder and 1.5g of samarium-based MOF powder in 100mL of acetone solution for 90min, heating and stirring to be nearly dry at the stirring speed of 180r/min, heating to 80 ℃, and drying in vacuum at 90 ℃ for 24h to obtain mixed powder; sintering at high temperature and high pressure by adopting spark plasma sintering, wherein the sintering process comprises the following steps: and the sintering temperature rise rate is 60 ℃/min, the sintering pressure is 4MPa, the sintering temperature is 1100 ℃, and the sintering time is 30min, so that the electrode is prepared.
Ti of 1 μm diameter 4 O 7 The powder was purchased from new materials, inc. of Lihebo, beijing.
Adding 0.89g of samarium nitrate hexahydrate and 0.64g of 2, 5-furandicarboxylic acid into a polytetrafluoroethylene reaction kettle containing 50mLN and N-dimethylformamide solvents, carrying out ultrasonic oscillation for 30min, then placing the reaction kettle into a constant-temperature drying box, preserving the temperature for 24h at 120 ℃, naturally cooling to room temperature after the reaction is finished, respectively washing for 2-3 times by using N, N-dimethylformamide and ethanol in sequence, and then carrying out vacuum drying for 12h at 90 ℃, thus obtaining the samarium-based MOF powder.
Example 4
MOF-Ti doped with rare earth metal 4 O 7 The preparation method of the composite electrode comprises the following specific steps:
1.5g of Ti having a diameter of 1 μm were taken 4 O 7 Ultrasonically mixing the powder and 1.5g of cerium-based MOF powder in 100mL of acetone solution for 90min, heating and stirring to be nearly dry at the stirring speed of 180r/min, heating to 80 ℃, and drying in vacuum at 90 ℃ for 24h to obtain mixed powder; sintering at high temperature and high pressure by adopting spark plasma sintering, wherein the sintering process comprises the following steps: the sintering temperature rise rate is 60 ℃/min, the sintering pressure is 4MPa, and the sintering temperature is 1100 DEG CAnd (3) sintering at the temperature of 30min to obtain the electrode.
Ti of 1 μm diameter 4 O 7 The powder was purchased from new materials, inc. of Lihebo, beijing.
The preparation of cerium-based MOF powder comprises the steps of dissolving 1.08g of cerium nitrate hexahydrate in 20mLN and N-dimethylformamide to obtain a metal salt solution, dissolving 1.05g of trimesic acid in 40mLN and N-dimethylformamide to obtain a ligand solution, slowly and dropwise adding the latter into the former solution under room temperature stirring, continuously stirring for 1 hour, adding ammonia water to adjust the pH value of the solution to 4.1, transferring the mixed solution to a polytetrafluoroethylene reaction kettle, placing the reaction kettle in a constant-temperature drying box, preserving the temperature for 18 hours at 100 ℃, naturally cooling to room temperature after the reaction is finished, sequentially washing for 1-3 times by using N, N-dimethylformamide and ethanol, and then carrying out vacuum drying for 12 hours at 150 ℃ to obtain the cerium-based MOF powder.
Example 5
MOF-Ti doped with rare earth metal 4 O 7 The preparation method of the composite electrode comprises the following specific steps:
10g of diethylenetriamine, 12gN, N-methylene-bisacrylamide, 30gN and N-dimethylformamide are taken to react for 23 hours at 65 ℃ to obtain the amino-terminated branched polymer.
5g of polyvinyl alcohol and 100mL of dimethyl sulfoxide are taken and uniformly stirred at 53 ℃, 0.2g of triethylamine and 0.6g of succinic anhydride are added for reaction for 2 hours, 0.6g of N-hydroxysuccinimide and 1g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride are added for reaction for 30 minutes, 30mL of amino-terminated branched polymer is added, and stirring is carried out for 24 hours, so as to obtain the modified polyvinyl alcohol.
Adding 0.6g of sodium dodecyl benzene sulfonate, 0.5g of hexadecyl trimethyl ammonium bromide and 100mL of deionized water into 10g of modified polyvinyl alcohol, uniformly stirring, adding 7g of butyraldehyde and hydrochloric acid, cooling, controlling the temperature to be 9 ℃, controlling the reaction time to be 1.2h, and adjusting the pH value to be 8.5 after the reaction is finished to obtain the auxiliary agent.
0.4g of diatomite and 2g of auxiliary agent are taken and stirred evenly, and 0.8g of Ti with the diameter of 100nm is added 4 O 7 The powder and 0.8g terbium-based MOF powder are mixed evenly in 50mL acetone solution by ultrasound for 30min, heated and stirred to be nearly dry, and the stirring speed is 150r/min, heating at 60 ℃, drying in vacuum at 70 ℃ for 10 hours to obtain mixed powder; sintering at high temperature and high pressure by adopting spark plasma sintering, wherein the heating rate is 50 ℃/min, the sintering pressure is 2MPa, the sintering temperature is 1000 ℃, and the sintering time is 20min, so as to prepare the electrode.
Ti of 100nm diameter 4 O 7 The powder was purchased from new materials, inc. of Lihebo, beijing.
Example 6
MOF-Ti doped with rare earth metal 4 O 7 The preparation method of the composite electrode comprises the following specific steps:
10g of diethylenetriamine, 12gN, N-methylene bisacrylamide, 30gN, N-dimethylformamide are taken to react for 22h at the temperature of 60 ℃, and the amino-terminated branched polymer is obtained.
5g of polyvinyl alcohol and 100mL of dimethyl sulfoxide are taken and uniformly stirred at 50 ℃, 0.2g of triethylamine and 0.6g of succinic anhydride are added for reaction for 1.5h, 0.6g of N-hydroxysuccinimide and 1g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride are added for reaction for 20min, 30mL of amino-terminated branched polymer is added, and stirring is carried out for 22h, so as to obtain the modified polyvinyl alcohol.
Adding 0.6g of sodium dodecyl benzene sulfonate, 0.5g of hexadecyl trimethyl ammonium bromide and 100mL of deionized water into 10g of modified polyvinyl alcohol, uniformly stirring, adding 7g of butyraldehyde and hydrochloric acid, cooling to 8 ℃, reacting for 1h, and adjusting the pH to 8 after the reaction is finished to obtain the assistant.
0.4g of diatomite and 2g of auxiliary agent are taken and stirred evenly, 1.0g of Ti with the diameter of 0.5 mu m 4 O 7 Uniformly mixing the powder and 1.0g of yttrium-based MOF powder in 80mL of acetone solution, carrying out ultrasonic treatment for 60min, heating and stirring until the mixture is nearly dried, wherein the stirring speed is 170r/min, the heating temperature is 70 ℃, carrying out vacuum drying for 80 ℃, and carrying out drying for 18h to obtain mixed powder; sintering at high temperature and high pressure by adopting spark plasma sintering, wherein the sintering process comprises the following steps: sintering at a temperature rise rate of 60 ℃/min, a sintering pressure of 3MPa, a sintering temperature of 1100 ℃ and a sintering time of 30min to obtain the electrode.
0.5 μm of Ti 4 O 7 The powder was purchased from beijing lihebo new materials ltd.
Example 7
MOF-Ti doped with rare earth metal 4 O 7 The preparation method of the composite electrode comprises the following specific steps:
10g of diethylenetriamine, 12gN, N-methylene-bisacrylamide, 30gN and N-dimethylformamide are taken to react for 22 to 24 hours at the temperature of 70 ℃, and the amino-terminated branched polymer is obtained.
5g of polyvinyl alcohol and 100mL of dimethyl sulfoxide are taken and uniformly stirred at 50-55 ℃, 0.2g of triethylamine and 0.6g of succinic anhydride are added for reaction for 2.5 hours, 0.6g of N-hydroxysuccinimide and 1g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride are added for reaction for 40 minutes, 30mL of amino-terminated branched polymer is added, and stirring is carried out for 26 hours, so as to obtain the modified polyvinyl alcohol.
Adding 0.6g of sodium dodecyl benzene sulfonate, 0.5g of hexadecyl trimethyl ammonium bromide and 100mL of deionized water into 10g of modified polyvinyl alcohol, uniformly stirring, adding 7g of butyraldehyde and hydrochloric acid, cooling, reacting for 1.5 hours at the temperature of 10 ℃, and adjusting the pH to be 9 after the reaction is finished to obtain the auxiliary agent.
0.4g of diatomite and 2g of auxiliary agent are taken and stirred evenly, and 1.5g of Ti with the diameter of 1 mu m is added 4 O 7 Uniformly mixing the powder and 1.5g of samarium-based MOF powder in 100mL of acetone solution, carrying out ultrasonic treatment for 90min, heating and stirring until the mixture is nearly dry, wherein the stirring speed is 180r/min, the heating temperature is 80 ℃, carrying out vacuum drying for 90 ℃, and carrying out drying for 24h to obtain mixed powder; sintering at high temperature and high pressure by adopting spark plasma sintering, wherein the sintering process comprises the following steps: sintering at 60 deg.C/min under 4MPa at 1100 deg.C for 30min to obtain the final product.
Ti of 1 μm diameter 4 O 7 The powder was purchased from new materials, inc. of Lihebo, beijing.
Comparative example 1
Ti 4 O 7 The preparation method of the electrode comprises the following specific steps:
taking 0.8g of Ti with the diameter of 100nm 4 O 7 Ultrasonically mixing the powder in 50mL of acetone solution for 30min, heating and stirring to near dryness at a stirring speed of 150r/min, heating to 60 deg.C, vacuum drying at 70 deg.C for 10h to obtain a mixtureMixing the powder; and sintering at high temperature and high pressure by adopting discharge plasma sintering, wherein the heating rate is 50 ℃/min, the sintering pressure is 2MPa, the sintering temperature is 1000 ℃, and the sintering time is 20min, so that the electrode is prepared.
Ti of 100nm diameter 4 O 7 The powder was purchased from new materials, inc. of Lihebo, beijing.
Comparative example 2
Rare earth metal doped Ti 4 O 7 The preparation method of the electrode comprises the following specific steps:
taking 0.8g of Ti with the diameter of 100nm 4 O 7 Ultrasonically mixing the powder and 0.3g of cerium chloride in 50mL of acetone solution for 30min, heating and stirring to be nearly dry, stirring at the speed of 150r/min, heating at the temperature of 60 ℃, and drying in vacuum at the temperature of 70 ℃ for 10h to obtain mixed powder; and sintering at high temperature and high pressure by adopting discharge plasma sintering, wherein the heating rate is 50 ℃/min, the sintering pressure is 2MPa, the sintering temperature is 1000 ℃, and the sintering time is 20min, so that the electrode is prepared.
Cerium chloride was purchased from alatin reagent (shanghai) ltd, cerium chloride heptahydrate.
Experiment of
Taking example 1 as a comparison, setting comparative example 1 and comparative example 2, wherein comparative example 1 is not added with rare earth MOF and is not added with rare earth metal salt, and comparative example 2 is not added with rare earth MOF, and carrying out a control experiment. The electrode samples obtained in examples 1 to 7 and comparative examples 1 to 2 were used as anodes, and the performance thereof was measured and the measurement results were recorded, respectively:
a test sample was taken as an anode, and an OH yield test experiment was performed by coumarin and terephthalic acid. Wherein, coumarin and terephthalic acid can both freely react with OH to respectively generate 7-hydroxycoumarin and 2-hydroxyterephthalic acid, and both can resist direct oxidation, so that the product concentration of 7-hydroxycoumarin and 2-hydroxyterephthalic acid can react with the generation rate of OH. Therefore, the reaction solution conditions were set as: the initial concentration of coumarin is 1mM, the initial concentration of terephthalic acid is 0.1mM, and the current density is 20mA/cm 2 The supporting electrolyte is 20mM Na 2 SO 4 Solution, reaction for 40min and detectionThe concentrations at which 7-hydroxycoumarin and 2-hydroxyterephthalic acid were produced, reported as OH-producing capacity (μ M), and the results of the tests are given in the following table;
a sample is taken as an anode, and an electrocatalytic efficiency evaluation experiment is carried out by taking 1, 4-dioxane as a model pollutant. The conditions of the reaction solution were set as follows: 1, 4-Dioxane initial concentration 1mM, supporting electrolyte 20mM Na 2 SO 4 Solution, current density 20mA/cm 2 The time taken for the removal rate of 1, 4-dioxane to reach 95% was measured, and the test results are shown in the following table.
And (4) conclusion: as can be seen from the test results in the table, ti prepared in comparison with comparative example 1 was used 4 O 7 Electrode, rare earth doped Ti prepared in comparative example 2 4 O 7 The electrode has higher OH production capacity and 1, 4-dioxane degradation performance, and the rare earth metal doping is favorable for enhancing Ti 4 O 7 Electrocatalytic activity of the electrode; the addition of the rare earth MOF is proved to further remarkably improve the catalytic activity of the electrode, and meanwhile, the improvement of the catalytic activity of the electrode due to the introduction of the rare earth MOF is far better than that of the pure rare earth metal salt doping in the preparation process of the electrode. Examples 5 to 7 the addition of the auxiliary agent and the diatomaceous earth further improves the catalytic activity of the electrode.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described above, or equivalents may be substituted for elements thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. MOF-Ti doped with rare earth metal 4 O 7 The preparation method of the composite electrode is characterized by comprising the following steps: the method comprises the following steps:
taking diatomite and an auxiliary agent, stirring uniformly, and adding Ti 4 O 7 The powder, the rare earth MOFs powder and the acetone solution are uniformly mixed by ultrasound, heated and stirred, and dried in vacuum to obtain mixed powder, high-temperature sintering is carried out by utilizing a spark plasma sintering technology, the temperature rising rate of the spark plasma sintering is 50-60 ℃/min, the sintering temperature is 1000-1100 ℃, the sintering time is 20-30min, and the sintering pressure is 2-4MPa, so that the electrode is prepared.
2. A rare earth metal doped MOF-Ti according to claim 1 4 O 7 The preparation method of the composite electrode is characterized by comprising the following steps: the rare earth metal in the rare earth MOFs powder is any one or more of lanthanum, cerium, praseodymium, terbium, yttrium, neodymium, promethium, samarium, europium and gadolinium.
3. A rare earth metal doped MOF-Ti according to claim 1 4 O 7 The preparation method of the composite electrode is characterized by comprising the following steps: the Ti 4 O 7 The powder has a diameter of 100nm-1 μm.
4. A rare earth metal doped MOF-Ti according to claim 1 4 O 7 The preparation method of the composite electrode is characterized by comprising the following steps: the mixed powder comprises the following components: 0.4-0.8 part of diatomite, 2-3.5 parts of auxiliary agent and 0.8-1.5 parts of Ti 4 O 7 Powder, 0.8-1.5 parts of rare earth MOFs powder.
5. A rare earth metal doped MOF-Ti according to claim 1 4 O 7 The preparation method of the composite electrode is characterized by comprising the following steps: the ultrasonic mixing time is 30-90min.
6. According toA rare earth metal doped MOF-Ti of claim 1 4 O 7 The preparation method of the composite electrode is characterized by comprising the following steps: the heating and stirring speed is 150-180r/min, and the heating temperature is 60-80 ℃.
7. A rare earth metal doped MOF-Ti according to claim 1 4 O 7 The preparation method of the composite electrode is characterized by comprising the following steps: the vacuum drying temperature is 70-90 ℃, and the drying time is 10-24h.
8. A rare earth metal doped MOF-Ti according to claim 1 4 O 7 The preparation method of the composite electrode is characterized by comprising the following steps: the preparation method of the auxiliary agent comprises the following steps: adding sodium dodecyl benzene sulfonate, hexadecyl trimethyl ammonium bromide and deionized water into modified polyvinyl alcohol, stirring uniformly, adding butyraldehyde and hydrochloric acid, cooling to 8-10 ℃, reacting for 1-1.5h, and adjusting the pH to 8-9 after the reaction is finished to obtain the assistant.
9. A rare earth metal doped MOF-Ti according to claim 8 4 O 7 The preparation method of the composite electrode is characterized by comprising the following steps: the preparation method of the modified polyvinyl alcohol comprises the following steps: uniformly stirring polyvinyl alcohol and dimethyl sulfoxide at 50-55 ℃, adding triethylamine and succinic anhydride, reacting for 1.5-2.5h, adding N-hydroxysuccinimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, reacting for 20-40min, adding an amino-terminated branched polymer, and stirring for 22-26h to obtain the modified polyvinyl alcohol.
10. A rare earth metal doped MOF-Ti according to claim 9 4 O 7 The preparation method of the composite electrode is characterized by comprising the following steps: the preparation method of the amino-terminated branched polymer comprises the following steps: taking diethylenetriamine, N-methylene-bisacrylamide and N, N-dimethylformamide to react for 22-24h at the temperature of 60-70 ℃ to obtain the amino-terminated branched polymer.
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