CN113135755A - Flexible cerium acid rare earth high-entropy nanofiber ceramic membrane and preparation method and application thereof - Google Patents
Flexible cerium acid rare earth high-entropy nanofiber ceramic membrane and preparation method and application thereof Download PDFInfo
- Publication number
- CN113135755A CN113135755A CN202110403375.2A CN202110403375A CN113135755A CN 113135755 A CN113135755 A CN 113135755A CN 202110403375 A CN202110403375 A CN 202110403375A CN 113135755 A CN113135755 A CN 113135755A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- ceramic membrane
- entropy
- cerium
- salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 79
- 239000012528 membrane Substances 0.000 title claims abstract description 78
- 239000002121 nanofiber Substances 0.000 title claims abstract description 72
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 72
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 17
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002253 acid Substances 0.000 title abstract description 11
- -1 ceric acid rare earth Chemical class 0.000 claims abstract description 44
- 238000009987 spinning Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 6
- 230000005855 radiation Effects 0.000 claims abstract description 6
- 230000004888 barrier function Effects 0.000 claims abstract description 5
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims description 26
- 238000005245 sintering Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 14
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 14
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 14
- 150000000703 Cerium Chemical class 0.000 claims description 12
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 10
- 229910052691 Erbium Inorganic materials 0.000 claims description 8
- 229910052693 Europium Inorganic materials 0.000 claims description 8
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 229910052772 Samarium Inorganic materials 0.000 claims description 8
- 229910052775 Thulium Inorganic materials 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 8
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 8
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims description 8
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 8
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 8
- 229940012189 methyl orange Drugs 0.000 claims description 8
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 8
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052727 yttrium Inorganic materials 0.000 claims description 8
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000001782 photodegradation Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 229920002301 cellulose acetate Polymers 0.000 claims description 6
- 238000001523 electrospinning Methods 0.000 claims description 6
- 229920001432 poly(L-lactide) Polymers 0.000 claims description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 6
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- 229910052773 Promethium Inorganic materials 0.000 claims description 4
- 229910052771 Terbium Inorganic materials 0.000 claims description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical group [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 4
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 4
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052706 scandium Inorganic materials 0.000 claims description 4
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 4
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 4
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 3
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004626 polylactic acid Substances 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 150000003840 hydrochlorides Chemical class 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 150000002823 nitrates Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000835 fiber Substances 0.000 abstract description 11
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 5
- 238000011161 development Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 19
- 238000012360 testing method Methods 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 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 3
- JVYYYCWKSSSCEI-UHFFFAOYSA-N europium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JVYYYCWKSSSCEI-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 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 3
- 238000002835 absorbance Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 2
- PEYIBPJKEYRLDB-UHFFFAOYSA-N thulium(3+);trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Tm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PEYIBPJKEYRLDB-UHFFFAOYSA-N 0.000 description 2
- 102220538248 TATA box-binding protein-associated factor RNA polymerase I subunit C_A40W_mutation Human genes 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- SXJVNCWLEGIRSJ-UHFFFAOYSA-N erbium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SXJVNCWLEGIRSJ-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- XWFVFZQEDMDSET-UHFFFAOYSA-N gadolinium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XWFVFZQEDMDSET-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010453 quartz 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
- YSUBIGXLOCNYKB-UHFFFAOYSA-N scandium(3+) trinitrate hexahydrate Chemical compound O.O.O.O.O.O.[N+](=O)([O-])[O-].[Sc+3].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] YSUBIGXLOCNYKB-UHFFFAOYSA-N 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XIOPWXFTXDPBEY-UHFFFAOYSA-N ytterbium(3+);trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XIOPWXFTXDPBEY-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/50—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62218—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic films, e.g. by using temporary supports
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/56—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of cyclic compounds with one carbon-to-carbon double bond in the side chain
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3227—Lanthanum oxide or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3229—Cerium oxides or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/606—Drying
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6562—Heating rate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Structural Engineering (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Toxicology (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Electromagnetism (AREA)
- Optics & Photonics (AREA)
- Plasma & Fusion (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Fibers (AREA)
Abstract
The invention discloses a flexible ceric acid rare earth high-entropy nanofiber ceramic membrane and a preparation method and application thereof. According to the invention, a ceramic material high-entropy method is combined with an electrostatic spinning nano method, a spinning solution is creatively prepared from five or more rare earth elements at least containing cerium, and finally, the ceramic material is sintered to obtain the flexible high-entropy cerium acid rare earth nanofiber ceramic membrane, wherein the length-diameter ratio of the nanofibers is up to more than 250, and the fiber diameter is up to 80 nm. The successful preparation of the flexible high-entropy nano ceramic fiber membrane has great significance for the development of the technical fields of flexible ceramic fiber membranes, nano fibers, high-entropy ceramics and the like. The nano-fiber ceramic membrane prepared by the method has a wide application prospect in the fields of thermal barrier materials, energy catalysis, radiation protection and the like.
Description
Technical Field
The invention belongs to the technical field of high-entropy ceramics and electrostatic spinning, and particularly relates to a flexible cerium acid rare earth high-entropy nanofiber ceramic membrane and a preparation method and application thereof.
Background
High Entropy Ceramics (HECs) are receiving increasing attention as solid solutions of one-component compounds containing three or more main components in equimolar or near equimolar ratios because of their many excellent properties. Single-component compounds, the existing forms of high-entropy ceramics mainly comprise powder, blocks, coatings and fibers. However, research on high-entropy ceramic fibers and application research on high-entropy ceramic properties are still few, and particularly, a preparation technology of a flexible high-entropy nanofiber ceramic membrane is not reported yet. How to prepare the flexible high-entropy nanofiber ceramic fiber membrane with the characteristics of excellent nano-size effect, high specific surface area, high length-diameter ratio, excellent mechanical properties and the like makes the flexible high-entropy nanofiber ceramic fiber membrane have a wide application prospect in the fields of thermal barrier materials, energy catalysis, radiation protection, ultraviolet absorption and the like, and becomes a technical problem to be solved in the field.
Disclosure of Invention
In order to improve the technical problems, the invention provides a flexible ceric acid rare earth high-entropy nanofiber ceramic membrane and a preparation method and application thereof.
The present invention provides a ceramic membrane comprising nanofibers.
According to an embodiment of the invention, the nanofibres contain at least five rare earth elements including at least cerium (Ce) element.
For example, the rare earth element may also be selected from at least four of yttrium (Y), lanthanum (La), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), thulium (Tm), erbium (Er), and scandium (Sc); preferably four, five or more selected from yttrium (Y), lanthanum (La), europium (Eu), gadolinium (Gd), samarium (Sm), erbium (Er) and thulium (Tm).
According to an embodiment of the present invention, the nanofibers have an aspect ratio of greater than 250, such as an aspect ratio of 260-400.
According to an embodiment of the invention, the diameter of the nanofibers is at least 80nm, e.g. 80-1000nm, preferably 200-500nm, exemplary 80nm, 100nm, 150nm, 200nm, 300nm, 350nm, 400m, 500nm, 800nm, 1000 nm.
According to an embodiment of the present invention, the ceramic membrane is a flexible ceramic membrane, preferably a flexible nanofiber ceramic membrane, more preferably a flexible rare earth ceric acid high entropy nanofiber ceramic membrane.
Preferably, the ceramic membrane has a morphology substantially as shown in fig. 2.
According to an embodiment of the present invention, the ceramic membrane is prepared from the following raw material components in parts by weight: 0.5-5 parts of polymer template agent and 0.3-5 parts of rare earth salt;
the rare earth salt comprises at least five rare earth salts, and the five rare earth salts at least comprise cerium salt.
According to the embodiment of the invention, the ceramic membrane is prepared by preparing composite nano-fibers from raw materials including a high-molecular template agent and rare earth salt through electrostatic spinning, and then sintering the composite nano-fibers at high temperature to obtain the ceramic membrane.
According to an embodiment of the present invention, the polymeric template is selected from at least one of polyvinyl alcohol (PVA), Polyacrylonitrile (PAN), polyethylene oxide (PEO), polylactic acid (PLA), polyvinylpyrrolidone (PVP), polymethyl methacrylate (PMMA), poly-l-lactic acid (PLLA), polyvinyl chloride (PVC), Cellulose Acetate (CA), and Polycarbonate (PC), and the like, preferably polyethylene oxide (PEO) or polyvinylpyrrolidone (PVP).
According to one embodiment of the present invention, the weight average molecular weight of the polyvinyl alcohol (PVA) is 30000-70000; exemplary are 30000, 5000, 70000;
according to one embodiment of the present invention, the weight average molecular mass of the Polyacrylonitrile (PAN) is 130000-150000; exemplary are 130000, 140000, 150000;
according to one embodiment of the present invention, the weight average molecular mass of the polyethylene oxide (PEO) is 200000-1000000; exemplary are 200000, 500000, 1000000;
according to one embodiment of the present invention, the weight average molecular mass of the polylactic acid (PLA) is 100000-200000; exemplary are 100000, 150000, 200000;
according to one embodiment of the invention, the weight average molecular mass of the polyvinylpyrrolidone (PVP) is 360000-1300000; exemplary are 360000, 500000, 1000000, 1300000;
according to one embodiment of the present invention, the weight average molecular mass of the Polymethylmethacrylate (PMMA) is 100000-150000; exemplary are 100000, 130000, 150000;
according to one embodiment of the invention, the weight average molecular mass of the poly-L-lactic acid (PLLA) is 100000-200000; exemplary are 100000, 150000, 200000;
according to one embodiment of the present invention, the weight average molecular mass of the polyvinyl chloride (PVC) is 45000-150000; exemplary are 45000, 100000, 150000;
according to one embodiment of the invention, the weight average molecular mass of the Cellulose Acetate (CA) is 30000-100000; exemplary are 30000, 50000, 100000;
according to one embodiment of the present invention, the weight average molecular mass of the Polycarbonate (PC) is 20000-100000; exemplary are 200000, 50000, 100000.
According to an embodiment of the invention, said rare earth salt is selected, in addition to the cerium salt, from the nitrates and/or hydrochlorides of at least four of the following rare earth elements; the rare earth element may be selected from scandium (Sc), yttrium (Y), lanthanum (La), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), thulium (Tm), erbium (Er); preferably selected from yttrium (Y), lanthanum (La), europium (Eu), gadolinium (Gd), samarium (Sm), erbium (Er) and thulium (Tm).
According to an embodiment of the invention, the cerium salt is cerium nitrate and/or cerium chloride. Preferably, the molar ratio of any rare earth salt except the cerium salt to the cerium salt is (2/n): 2, n is the number of types of rare earth elements in the rare earth salt, and n is not less than 5 and is a natural number.
According to an embodiment of the invention, the molar ratio of any two rare earth salts other than the cerium salt is 1: 0.8 to 1.5, illustratively 1: 0.8, 1: 1, 1: 1.2, 1: 1.5.
According to an embodiment of the invention, the ceramic membrane has a softness of 20-120mN, e.g. 40mN, 55mN, 82 mN.
According to an embodiment of the invention, the ceramic membrane has a thermal conductivity of 0.020 to 0.080W/m.K, for example 0.030W/m.K, 0.045W/m.K, 0.053W/m.K.
According to an embodiment of the invention, the ceramic membrane has a 5h photo-degradation rate for dyes (e.g. methyl orange) of at least 68%, e.g. 69%, 69.5%, 71.2%, 75%, 80.6%, 85%.
The invention also provides a preparation method of the ceramic membrane, which comprises the following steps: the ceramic membrane is prepared by preparing composite nano-fibers from raw materials including a high-molecular template agent and rare earth salt through electrostatic spinning, and then sintering the composite nano-fibers at high temperature.
According to an embodiment of the present invention, the polymeric templating agent and the rare earth salt have the selection and ratio as shown above.
According to an embodiment of the invention, the preparation method comprises the steps of:
dissolving raw materials including a high-molecular template agent and rare earth salt in a solvent to obtain a spinning solution, performing electrostatic spinning to obtain composite nano-fibers, and sintering the composite nano-fibers at a high temperature to obtain the ceramic membrane.
According to an embodiment of the present invention, the solvent is selected from one, two or more of N, N-Dimethylformamide (DMF), ethanol, water, and the like. Preferably a mixed solvent of ethanol and water.
According to an embodiment of the invention, the mass fraction of the polymeric templating agent is 1-16%, illustratively 1%, 3.6%, 5%, 10%, 15%.
According to an embodiment of the invention, the rare earth salt is 5-22% of the total mass of the spinning dope, exemplarily 5%, 8%, 10%, 12%, 15%, 18%, 20%.
According to an embodiment of the present invention, the polymer template and the rare earth salt may be mixed in the form of a solution thereof or the rare earth salt and the polymer template may be sequentially added to a solvent to be mixed. For example, a mixed solution of rare earth salts is prepared, and then a polymer template is added to the mixed solution to obtain a spinning solution.
According to an embodiment of the present invention, the method further comprises the step of stirring the spinning solution to completely dissolve the raw materials. For example, the stirring time may be 4 to 8 hours; exemplary are 4h, 6h, 8 h.
According to an embodiment of the invention, the voltage of the electrospinning is 10-40kV, preferably 15-26kV, exemplary 15kV, 17kV, 19kV, 20kV, 22kV, 25kV, 26 kV.
According to an embodiment of the invention, the feed rate of the electrospinning is 0.2 to 1.8 mL-h-1Exemplary is 0.2 mL. h-1、0.5mL·h-1、0.8mL·h-1、1.0mL·h-1、1.5mL·h-1、1.6mL·h-1、1.8mL·h-1。
According to an embodiment of the invention, the spinning distance of said electrospinning is 5-16cm, exemplary 5cm, 8cm, 10cm, 13cm, 15 cm.
The "spinning distance" refers to the perpendicular distance of the injector outlet from the spin receiving matrix. For example, the receiving substrate may be an aluminum foil clad metal mold.
According to an embodiment of the present invention, the temperature of the high temperature sintering is 600-1600 ℃, and exemplary temperatures are 600 ℃, 800 ℃, 1000 ℃, 1200 ℃, 1500 ℃, 1600 ℃.
According to an embodiment of the invention, the high temperature sintering time is 1-3h, exemplary 1h, 2h, 3 h.
According to an embodiment of the invention, the temperature rise rate of the high temperature sintering is 0.1-10 ℃/min, exemplary 0.1 ℃/min, 2 ℃/min, 5 ℃/min, 10 ℃/min.
According to an embodiment of the present invention, the atmosphere of the high temperature sintering is an oxygen-containing atmosphere, for example, an air atmosphere.
According to an embodiment of the present invention, the composite nanofiber is further dried before the high-temperature sintering process. For example, the drying means may be vacuum drying. Further, the drying time is 2-5h, exemplary 2h, 3h, 5 h.
According to an embodiment of the present invention, the method for preparing the ceramic membrane comprises the steps of:
(1) dissolving rare earth salt in a solvent, and adding a high-molecular template agent to prepare a spinning solution;
(2) filling the spinning solution prepared in the step (1) into an injector, and adjusting the voltage, the feeding rate and the spinning distance of electrostatic spinning to prepare composite nano fibers;
(3) and (3) drying the composite nanofiber prepared in the step (2), and then sintering at a high temperature in an air atmosphere to prepare the ceramic membrane.
The invention also provides application of the ceramic membrane in the fields of thermal barrier materials, energy catalysis, radiation protection or ultraviolet absorption and the like.
The invention has the advantages of
(1) According to the invention, a ceramic material high-entropy method is combined with an electrostatic spinning nano method, a spinning solution is creatively prepared from five or more rare earth elements at least containing cerium, and finally, the ceramic material is sintered to obtain the flexible high-entropy cerium acid rare earth nanofiber ceramic membrane, wherein the length-diameter ratio of the nanofibers is up to more than 250, and the fiber diameter is up to 80 nm. The successful preparation of the flexible high-entropy nano ceramic fiber membrane has great significance for the development of the technical fields of flexible ceramic fiber membranes, nano fibers, high-entropy ceramics and the like.
(2) The ceric acid rare earth based high-entropy nanofiber ceramic membrane with good flexibility overcomes the brittleness of the traditional inorganic ceramic material.
(3) The cerium acid rare earth high-entropy rare earth nanofiber ceramic membrane prepared by the invention is simple in preparation process and can be produced in large scale, and the prepared nanofiber ceramic membrane has a wide application prospect in the fields of thermal barrier materials, energy catalysis, radiation protection and the like.
Drawings
Fig. 1 is a real object diagram of the flexible rare earth ceric acid high-entropy nanofiber ceramic membrane prepared in example 1.
FIG. 2 is an SEM image of the flexible rare earth cerate high-entropy nano-fiber prepared in example 1.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
In the following examples of the invention, the photocatalytic activity of the ceramic membrane was evaluated by methyl orange ultraviolet degradation. The specific experimental method is as follows:
A40W mercury lamp was used to provide a radiation source in the wavelength range 200 and 400 nm. In a quartz reaction vessel, the initial concentration of methyl orange was fixed at 20mg/L and the amount of catalyst added was 1 g/L. The degree of decomposition of methyl orange was determined by UV-721 spectrometer. The photodegradation rate was calculated by the following formula:
d＝(A0-Ai)/A0 (1)
in the formula, AiIs the absorbance value of methyl orange solution measured at 5h in the photodegradation process, A0Is the absorbance value of the original methyl orange solution.
Example 1
Dissolving 0.30g of lanthanum nitrate hexahydrate, 0.31g of gadolinium nitrate hexahydrate, 0.31g of europium nitrate hexahydrate, 0.31g of ytterbium nitrate pentahydrate, 0.26g of yttrium nitrate hexahydrate and 1.50g of cerium nitrate hexahydrate in 4.00g of water and 6.30g of ethanol until the solution is clear and transparent, adding 0.50g of polyvinylpyrrolidone (PVP, the weight-average molecular weight is 130 ten thousand) to prepare a solution, and continuing stirring for 4 hours. Then the spinning solution is filled into an injector, the voltage of the spinning is set to be 15kV, the feeding speed is set to be 0.20 mL.h-1And the spinning height is 15 cm. And collecting the spun composite nanofiber in a grounded aluminum foil coated metal mold, removing the composite nanofiber membrane, drying the composite nanofiber membrane at room temperature for 2 hours in vacuum, and heating to 600 ℃ at a heating rate of 2 ℃/min in an air atmosphere for sintering for 2 hours to obtain the ceric acid rare earth high-entropy nanofiber ceramic membrane.
Fig. 1 is a diagram of a cerium rare earth high-entropy nanofiber ceramic membrane prepared in this embodiment, and the result shows that the cerium rare earth high-entropy nanofiber ceramic membrane material prepared in the present invention has high flexibility.
The softness of the ceric acid rare earth high-entropy nano-fiber ceramic membrane prepared by the embodiment is measured to be 40mN by adopting a YT-RRY softness tester (the sample size is 10 multiplied by 10cm, the width of a crack of a sample table is 5mm, and the average value is obtained after 10 times of measurement).
Fig. 2 is a scanning electron microscope image of the rare earth cerate high-entropy nanofiber prepared in the embodiment, and the results in the image show that: the fiber diameter was about 300-400 nm.
The heat conductivity of the ceric acid rare earth high-entropy nanofiber ceramic membrane prepared in the embodiment is tested to be 0.030W/m.K by adopting a Hot-Disk test.
Through tests, the 5-hour photodegradation rate of the cerium acid rare earth high-entropy nanofiber ceramic membrane prepared in the embodiment to methyl orange is 80.6%.
Example 2
0.10g of lanthanum nitrate hexahydrate,0.08g of scandium nitrate hexahydrate, 0.10g of europium nitrate hexahydrate, 0.10g of thulium nitrate pentahydrate, 0.09g of yttrium nitrate hexahydrate and 0.50g of cerium nitrate hexahydrate are dissolved in 4.00g of water and 6.30g of ethanol until the solution is clear and transparent, 2.0g of polyvinylpyrrolidone (PVP, the weight-average molecular weight is 130 ten thousand) is added to prepare a solution, and the solution is continuously stirred for 4 hours. Then the spinning solution was filled into an injector, and the voltage of spinning was set to 26kV, the feed rate was set to 1.0 mL. multidot.h-1And the spinning height is 13 cm. And collecting the spun composite nanofiber in a grounded aluminum foil coated metal mold, removing the composite nanofiber membrane, drying the composite nanofiber membrane at room temperature for 2 hours in vacuum, and heating to 800 ℃ at a heating rate of 0.1 ℃/min in an air atmosphere for sintering for 2 hours to obtain the cerium acid rare earth high-entropy nanofiber ceramic membrane.
The softness of the ceric acid rare earth high-entropy nanofiber ceramic membrane prepared in the embodiment is measured to be 55mN (the sample size is 10 multiplied by 10cm, the width of a crack of a sample table is 5mm, and the average value is obtained after 10 times of measurement) by adopting a YT-RRY softness tester, and the thermal conductivity of the ceric acid rare earth high-entropy nanofiber ceramic membrane prepared in the embodiment is measured to be 0.045W/m.K by adopting Hot-Disk.
Through tests, the 5-hour photodegradation rate of the cerium acid rare earth high-entropy nanofiber ceramic membrane prepared in the embodiment to methyl orange is 71.2%.
Example 3
0.11g of erbium nitrate hexahydrate, 0.10g of samarium nitrate hexahydrate, 0.10g of europium nitrate hexahydrate, 0.10g of thulium nitrate pentahydrate, 0.08g of yttrium nitrate hexahydrate and 0.50g of cerium nitrate hexahydrate are dissolved in 6.00g of water and 4.73g of ethanol until the solution is clear and transparent, 2.00g of polyethylene oxide (PEO, the weight-average molecular weight is 100 ten thousand) is added to prepare a solution, and the solution is continuously stirred for 4 hours. Then the spinning solution was filled into an injector, and the voltage of spinning was set to 17kV, the feed rate was set to 1.6 mL. h-1And the spinning height is 5 cm. And collecting the spun composite nanofiber in a grounded aluminum foil coated metal mold, removing the composite nanofiber membrane, drying the composite nanofiber membrane at room temperature for 5 hours in vacuum, and heating to 1600 ℃ at a heating rate of 10 ℃/min in an air atmosphere for sintering for 2 hours to obtain the ceric acid rare earth high-entropy nanofiber ceramic membrane.
The softness of the ceric acid rare earth high-entropy nanofiber ceramic membrane prepared in the embodiment is measured to reach 82mN by adopting a YT-RRY softness tester (the sample size is 10 multiplied by 10cm, the width of a crack of a sample table is 5mm, and the average value is obtained after 10 times of measurement).
The heat conductivity of the cerium acid rare earth high-entropy nano-fiber ceramic membrane prepared in the embodiment is tested to be 0.053W/m.K by adopting a Hot-Disk test.
Through tests, the 5-hour photodegradation rate of the cerium acid rare earth high-entropy nanofiber ceramic membrane prepared in the embodiment to methyl orange is 69.5%.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. 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. A ceramic membrane, characterized in that it contains nanofibers.
Preferably, the nanofiber contains at least five rare earth elements, and the rare earth elements at least comprise cerium (Ce).
For example, the rare earth element may also be selected from at least four of yttrium (Y), lanthanum (La), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), thulium (Tm), erbium (Er), and scandium (Sc); preferably four, five or more selected from yttrium (Y), lanthanum (La), europium (Eu), gadolinium (Gd), samarium (Sm), erbium (Er) and thulium (Tm).
Preferably, the nanofibers have an aspect ratio of greater than 250, for example an aspect ratio of 260-400.
Preferably, the nanofibers have a diameter of at least 80 nm.
2. A ceramic membrane according to claim 1, wherein the ceramic membrane is prepared from raw material components comprising, by weight: 0.5-5 parts of polymer template agent and 0.3-5 parts of rare earth salt;
the rare earth salt comprises at least five rare earth salts, and the five rare earth salts at least comprise cerium salt.
Preferably, the ceramic membrane is a flexible ceramic membrane, preferably a flexible nanofiber ceramic membrane, and more preferably a flexible rare earth ceric acid high-entropy nanofiber ceramic membrane.
3. A ceramic membrane according to claim 1 or 2, wherein the ceramic membrane is prepared by electrospinning a raw material comprising a polymeric templating agent and a rare earth salt to obtain composite nanofibers, and sintering the composite nanofibers at a high temperature to obtain the ceramic membrane.
Preferably, the polymeric template is at least one selected from polyvinyl alcohol (PVA), Polyacrylonitrile (PAN), polyethylene oxide (PEO), polylactic acid (PLA), polyvinylpyrrolidone (PVP), polymethyl methacrylate (PMMA), poly-l-lactic acid (PLLA), polyvinyl chloride (PVC), Cellulose Acetate (CA), and Polycarbonate (PC), and the like, and is preferably polyethylene oxide (PEO) or polyvinylpyrrolidone (PVP).
Preferably, the rare earth salt is selected from nitrates and/or hydrochlorides of at least four of the following rare earth elements in addition to the cerium salt; the rare earth element may be selected from scandium (Sc), yttrium (Y), lanthanum (La), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), thulium (Tm), erbium (Er); preferably selected from yttrium (Y), lanthanum (La), europium (Eu), gadolinium (Gd), samarium (Sm), erbium (Er) and thulium (Tm).
Preferably, the cerium salt is cerium nitrate and/or cerium chloride. Preferably, the molar ratio of any rare earth salt except the cerium salt to the cerium salt is (2/n): 2, n is the number of types of rare earth elements in the rare earth salt, and n is not less than 5 and is a natural number.
Preferably, the molar ratio of any two rare earth salts other than the cerium salt is 1: (0.8-1.5).
Preferably, the softness of the ceramic membrane is 20-120 mN;
preferably, the ceramic membrane has a thermal conductivity of 0.020-0.080W/m.K;
preferably, the ceramic membrane has a 5h photo-degradation rate of at least 68% for a dye (e.g. methyl orange).
4. A method for the preparation of a ceramic membrane according to any of claims 1 to 3, comprising the steps of: the ceramic membrane is prepared by preparing composite nano-fibers from raw materials including a high-molecular template agent and rare earth salt through electrostatic spinning, and then sintering the composite nano-fibers at high temperature.
5. The method of claim 4, comprising the steps of:
dissolving raw materials including a high-molecular template agent and rare earth salt in a solvent to obtain a spinning solution, performing electrostatic spinning to obtain composite nano-fibers, and sintering the composite nano-fibers at a high temperature to obtain the ceramic membrane.
6. The method according to claim 5, wherein the solvent is one, two or more selected from the group consisting of N, N-Dimethylformamide (DMF), ethanol, water and the like. Preferably a mixed solvent of ethanol and water.
7. The method according to claim 5 or 6, wherein the mass fraction of the polymer template is 1 to 16%.
Preferably, the rare earth salt accounts for 5-22% of the total mass of the spinning solution.
8. The production method according to any one of claims 5 to 7, wherein the voltage for electrospinning is 10 to 40 kV.
Preferably, the feed rate of the electrospinning is 0.2-1.8 mL-h-1。
Preferably, the spinning distance of the electrostatic spinning is 5-16 cm.
Preferably, the temperature of the high-temperature sintering is 600-1600 ℃.
Preferably, the time of the high-temperature sintering is 1-3 h.
Preferably, the heating rate of the high-temperature sintering is 0.1-10 ℃/min.
9. The method of any one of claims 5 to 8, wherein the ceramic membrane is prepared by a method comprising the steps of:
(1) dissolving rare earth salt in a solvent, and adding a high-molecular template agent to prepare a spinning solution;
(2) filling the spinning solution prepared in the step (1) into an injector, and adjusting the voltage, the feeding rate and the spinning distance of electrostatic spinning to prepare composite nano fibers;
(3) and (3) drying the composite nanofiber prepared in the step (2), and then sintering at a high temperature in an air atmosphere to prepare the ceramic membrane.
10. Use of a ceramic membrane according to any of claims 1 to 3 and/or a ceramic membrane obtained by a method according to any of claims 4 to 9 in the fields of thermal barrier materials, energy catalysis, radiation protection or uv absorption.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110403375.2A CN113135755B (en) | 2021-04-14 | 2021-04-14 | Flexible cerium acid rare earth high-entropy nanofiber ceramic membrane and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110403375.2A CN113135755B (en) | 2021-04-14 | 2021-04-14 | Flexible cerium acid rare earth high-entropy nanofiber ceramic membrane and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113135755A true CN113135755A (en) | 2021-07-20 |
| CN113135755B CN113135755B (en) | 2023-03-17 |
Family
ID=76812876
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110403375.2A Active CN113135755B (en) | 2021-04-14 | 2021-04-14 | Flexible cerium acid rare earth high-entropy nanofiber ceramic membrane and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113135755B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114751737A (en) * | 2021-08-19 | 2022-07-15 | 厦门稀土材料研究所 | Zirconic acid rare earth-based high-entropy ceramic nanofiber and preparation method and application thereof |
| CN115286809A (en) * | 2022-08-11 | 2022-11-04 | 西北工业大学 | Flexible rare earth zirconate high-entropy ceramic fiber membrane and preparation and application thereof |
| CN115467048A (en) * | 2022-09-21 | 2022-12-13 | 山东大学 | High-entropy rare earth niobate or tantalate ceramic fiber and preparation method thereof |
| CN115838993A (en) * | 2022-12-13 | 2023-03-24 | 南京邮电大学 | High-infrared-radiation fiber felt and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104153124A (en) * | 2014-07-30 | 2014-11-19 | 东华大学 | Flexible rare-earth oxide nanofiber membrane and preparation method thereof |
| US20180100249A1 (en) * | 2016-10-11 | 2018-04-12 | University Of Massachusetts | Polymer nanofibers from electrospinning of complex coacervates, and compositions and methods thereof |
| CN111592361A (en) * | 2020-04-09 | 2020-08-28 | 中国科学院化学研究所 | Nitride high-entropy ceramic fiber and preparation method and application thereof |
| CN111592358A (en) * | 2020-04-09 | 2020-08-28 | 中国科学院化学研究所 | Carbide high-entropy ceramic fiber and preparation method thereof |
| CN111763087A (en) * | 2020-06-29 | 2020-10-13 | 西安交通大学 | Series of cubic fluorite type high-entropy cerium oxide nano-powder and preparation method thereof |
-
2021
- 2021-04-14 CN CN202110403375.2A patent/CN113135755B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104153124A (en) * | 2014-07-30 | 2014-11-19 | 东华大学 | Flexible rare-earth oxide nanofiber membrane and preparation method thereof |
| US20180100249A1 (en) * | 2016-10-11 | 2018-04-12 | University Of Massachusetts | Polymer nanofibers from electrospinning of complex coacervates, and compositions and methods thereof |
| CN111592361A (en) * | 2020-04-09 | 2020-08-28 | 中国科学院化学研究所 | Nitride high-entropy ceramic fiber and preparation method and application thereof |
| CN111592358A (en) * | 2020-04-09 | 2020-08-28 | 中国科学院化学研究所 | Carbide high-entropy ceramic fiber and preparation method thereof |
| CN111763087A (en) * | 2020-06-29 | 2020-10-13 | 西安交通大学 | Series of cubic fluorite type high-entropy cerium oxide nano-powder and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 刘莉: "静电纺丝法制备Y2O3纳米纤维与表征", 《中国稀土学报》 * |
| 杨鸣波: "《塑料成型工艺学 第3版》", 30 June 2014, 中国轻工业出版社 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114751737A (en) * | 2021-08-19 | 2022-07-15 | 厦门稀土材料研究所 | Zirconic acid rare earth-based high-entropy ceramic nanofiber and preparation method and application thereof |
| CN114751737B (en) * | 2021-08-19 | 2024-06-18 | 厦门稀土材料研究所 | Rare earth zirconate-based high-entropy ceramic nanofiber and preparation method and application thereof |
| CN115286809A (en) * | 2022-08-11 | 2022-11-04 | 西北工业大学 | Flexible rare earth zirconate high-entropy ceramic fiber membrane and preparation and application thereof |
| CN115467048A (en) * | 2022-09-21 | 2022-12-13 | 山东大学 | High-entropy rare earth niobate or tantalate ceramic fiber and preparation method thereof |
| CN115467048B (en) * | 2022-09-21 | 2023-11-17 | 山东大学 | High-entropy rare earth niobate or tantalate ceramic fiber and preparation method thereof |
| CN115838993A (en) * | 2022-12-13 | 2023-03-24 | 南京邮电大学 | High-infrared-radiation fiber felt and preparation method thereof |
| CN115838993B (en) * | 2022-12-13 | 2023-09-15 | 南京邮电大学 | High infrared radiation fiber mat and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113135755B (en) | 2023-03-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113135755B (en) | Flexible cerium acid rare earth high-entropy nanofiber ceramic membrane and preparation method and application thereof | |
| US4797378A (en) | Internally modified ceramic fiber | |
| CN108893863B (en) | ZIF-8/polyvinylidene fluoride composite nanofiber membrane and preparation method and application thereof | |
| CA1276761C (en) | Bicomponent ceramic fibers | |
| JP2007529645A (en) | Active and adaptable photochromic fibers, fabrics and membranes | |
| Zhang et al. | Electrospinning preparation and luminescence properties of Eu (TTA) 3phen/polystyrene composite nanofibers | |
| US5837011A (en) | Method for making metal oxide textiles for spectral emitters | |
| WO2021159646A1 (en) | Lanthanide rare earth-organic polymer precursor, lanthanide rare earth oxide fiber, preparation method therefor and application thereof | |
| CN108315838B (en) | Method for preparing yttrium oxide nano-fiber by yttrium polymer precursor | |
| CN1664187A (en) | Regenerable reclaiming type polyvinyl alcohol nano fabric and method for making same | |
| CN113089132B (en) | Zirconate fiber and preparation method thereof | |
| CN109433024A (en) | Membrane material or aerogel material containing metal organic framework nanofiber and the preparation method and application thereof | |
| CN102309930A (en) | Preparation method of polyphenylene sulfide ultra-fine fiber porous membrane | |
| US20090068466A1 (en) | Titania fiber and method for manufacturing titania fiber | |
| CN114751737A (en) | Zirconic acid rare earth-based high-entropy ceramic nanofiber and preparation method and application thereof | |
| EP2103722B1 (en) | Ceramic fiber and method for production of ceramic fiber | |
| CN106835356B (en) | A method of preparing cobalt protoxide hollow nano fiber | |
| CN108547009A (en) | A kind of nano fluorescence fiber material and preparation method thereof | |
| CN104928789B (en) | Electrostatic spinning combination anti-solvent technology prepares porous nano-fibre and preparation method | |
| CN108103609B (en) | Dual-wavelength fluorescent anti-counterfeiting composite nanofiber with phase change function and preparation method thereof | |
| CN102392322A (en) | Method for preparing europium-doped sulfur oxide gadolinium light-emitting nanometer fiber | |
| TW201714667A (en) | Manufacturing method of photocatalyst composite nanofiber capable of effectively absorbing and degrading organic pollutants in waste water through visible light | |
| CN102817114B (en) | Method for preparing europium-doped octafluoro yttrium barium red luminescent nano-fiber | |
| CN109868526B (en) | Method for preparing yttrium zirconate nanofiber by using zirconium-yttrium polymer precursor | |
| CN109750388B (en) | Preparation method of defect fluorite phase gadolinium zirconate fiber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |