CN113135755B - 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
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- CN113135755B CN113135755B CN202110403375.2A CN202110403375A CN113135755B CN 113135755 B CN113135755 B CN 113135755B CN 202110403375 A CN202110403375 A CN 202110403375A CN 113135755 B CN113135755 B CN 113135755B
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- rare earth
- ceramic membrane
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- 239000000919 ceramic Substances 0.000 title claims abstract description 86
- 239000012528 membrane Substances 0.000 title claims abstract description 83
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 73
- 239000002121 nanofiber Substances 0.000 title claims abstract description 71
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 15
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 150000002910 rare earth metals Chemical class 0.000 title abstract description 11
- 239000002253 acid Substances 0.000 title abstract description 8
- -1 ceric acid rare earth Chemical class 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000009987 spinning Methods 0.000 claims abstract description 26
- 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 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 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 13
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 10
- 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
- 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 group [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
- 239000002904 solvent Substances 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
- 238000001782 photodegradation Methods 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
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 5
- 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
- 150000002823 nitrates Chemical group 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims 2
- 150000001805 chlorine compounds Chemical class 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 18
- 238000010438 heat treatment Methods 0.000 description 6
- 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
- 238000003756 stirring Methods 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
- 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
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 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
- 238000005259 measurement Methods 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
- 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
- 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
- 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
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 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
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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 80nm. 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 invention, the nanofibers have an aspect ratio of greater than 250, for example an aspect ratio of 260 to 400.
According to an embodiment of the invention, the diameter of the nanofibers is at least 80nm, such as 80-1000nm, preferably 200-500nm, exemplary 80nm, 100nm, 150nm, 200nm, 300nm, 350nm, 400m, 500nm, 800nm, 1000nm.
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 polyvinyl alcohol (PVA) has a weight average molecular weight of 30000 to 70000; exemplary are 30000, 5000, 70000;
according to one embodiment of the invention, the Polyacrylonitrile (PAN) has a weight average molecular mass of 130000 to 150000; exemplary are 130000, 140000, 150000;
according to one embodiment of the invention, the polyethylene oxide (PEO) has a weight average molecular mass of 200000 to 1000000; exemplary are 200000, 500000, 1000000;
according to one embodiment of the invention, the weight average molecular mass of the polylactic acid (PLA) is from 100000 to 200000; exemplary are 100000, 150000, 200000;
according to one embodiment of the invention, the polyvinylpyrrolidone (PVP) has a weight average molecular mass of 360000-1300000; exemplary are 360000, 500000, 1000000, 1300000;
according to one embodiment of the invention, the weight average molecular mass of the Polymethylmethacrylate (PMMA) is 100000 to 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 from 100000 to 200000; exemplary are 100000, 150000, 200000;
according to one embodiment of the 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 Cellulose Acetate (CA) has a weight average molecular mass of 30000 to 100000; exemplary are 30000, 50000, 100000;
according to one embodiment of the invention, the weight average molecular mass of the Polycarbonate (PC) is 20000 to 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) to 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, 82mN.
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 a dye (e.g. methyl orange) of at least 68%, such as 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 firstly preparing composite nano-fibers from raw materials comprising 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 present 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, 8h.
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, 26kV.
According to an embodiment of the invention, the feed rate of the electrospinning is 0.2 to 1.8 mL-h -1 Illustrative 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, 15cm.
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 invention, the high temperature sintering temperature is 600-1600 ℃, exemplary 600 ℃, 800 ℃, 1000 ℃, 1200 ℃, 1500 ℃, 1600 ℃.
According to the embodiment of the invention, the high-temperature sintering time is 1-3h, and is exemplified by 1h, 2h and 3h.
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, 5h.
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 80nm. 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 quantities, 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 nanofiber 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 techniques realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise specified, 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:
a 40W mercury lamp was used to provide a source of radiation in the wavelength range 200-400 nm. In a quartz reaction vessel, the initial concentration of methyl orange was fixed at 20mg/L, and the amount of catalyst added was 1g/L. The degree of decomposition of methyl orange was determined by UV-721 spectrometer. The photodegradation rate was calculated by the following formula:
d＝(A 0 -A i )/A 0 (1)
in the formula, A i Is the absorbance value of methyl orange solution measured at 5h in the photodegradation process, A 0 Is 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- 1 And the spinning height is 15cm. Collecting the spun composite nanofiber in a grounded aluminum foil coated metal mold, removing a composite nanofiber membrane, drying the composite nanofiber membrane at room temperature for 2h in vacuum, and heating to 600 ℃ at a heating rate of 2 ℃/min in an air atmosphere for sintering for 2h to obtain the ceric acid rare earth high-entropy nanofiberAnd (3) a vitamin 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 is about 300-400nm.
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 testing, the 5-hour photodegradation rate of the ceric acid rare earth high-entropy nanofiber ceramic membrane on methyl orange is 80.6%.
Example 2
Dissolving 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 in 4.00g of water and 6.30g of ethanol until the solution is clear and transparent, adding 2.0g of polyvinylpyrrolidone (PVP, weight-average molecular weight of 130 ten thousand) to prepare a solution, and continuing stirring 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 -1 And the spinning height is 13cm. 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 testing, the 5-hour photodegradation rate of the ceric acid rare earth high-entropy nanofiber ceramic membrane on 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 for spinning was set at 17kV and the feed rate was set at 1.6 mL. H -1 And the spinning height is 5cm. 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 cerium acid rare earth high-entropy nanofiber ceramic membrane.
The softness of the ceric acid rare earth high-entropy nano-fiber ceramic membrane prepared in the embodiment is measured to be 82mN by adopting a YT-RRY softness tester (the size of a sample is 10 multiplied by 10cm, the width of a crack of a sample table is 5mm, and the average value is obtained by measuring 10 times).
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 testing, the 5-hour photodegradation rate of the ceric acid rare earth high-entropy nanofiber ceramic membrane on 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 without departing from the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (28)
1. A flexible ceric acid rare earth high-entropy nanofiber ceramic membrane is characterized in that the ceramic membrane contains nanofibers;
the nanofibers contain at least five rare earth elements including at least cerium (Ce) element and further including at least four elements selected from the group consisting 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);
the aspect ratio of the nanofibers is greater than 250;
the diameter of the nanofiber is at least 80nm;
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;
the rare earth salt is selected from nitrates and/or hydrochlorides of at least four rare earth elements as follows besides cerium salt; the rare earth element is 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);
the atmosphere of the high-temperature sintering is oxygen-containing atmosphere.
2. The ceramic film of claim 1, wherein the rare earth elements comprise at least cerium (Ce) and further comprise four, five or more selected from yttrium (Y), lanthanum (La), europium (Eu), gadolinium (Gd), samarium (Sm), erbium (Er) and thulium (Tm).
3. The ceramic membrane of claim 1, wherein the nanofibers have an aspect ratio of 260 to 400.
4. A ceramic membrane according to any one of claims 1 to 3, wherein the ceramic membrane is prepared from raw material components comprising, 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.
5. The ceramic membrane of claim 4, wherein the polymeric templating agent is selected from at least one of polyvinyl alcohol (PVA), polyacrylonitrile (PAN), polyethylene oxide (PEO), polylactic acid (PLA), polyvinyl pyrrolidone (PVP), polymethyl methacrylate (PMMA), poly-L-lactic acid (PLLA), polyvinyl chloride (PVC), cellulose Acetate (CA), and Polycarbonate (PC).
6. The ceramic membrane of claim 5, wherein the polymeric templating agent is polyethylene oxide (PEO) or polyvinylpyrrolidone (PVP).
7. A ceramic film according to claim 1, wherein the rare earth salt is selected from the nitrates and/or chlorides of four rare earth elements of yttrium (Y), lanthanum (La), europium (Eu), gadolinium (Gd), samarium (Sm), erbium (Er) and thulium (Tm) in addition to the cerium salt.
8. A ceramic membrane according to claim 1, wherein the cerium salt is cerium nitrate and/or cerium chloride.
9. The ceramic membrane according to claim 1, wherein the molar ratio of any rare earth salt other than 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.
10. A ceramic membrane according to claim 1 or 9, wherein the molar ratio of any two rare earth salts other than the cerium salt is 1 (0.8-1.5).
11. A ceramic membrane according to claim 1, having a softness of 20-120mN.
12. A ceramic membrane according to claim 1 or 11, wherein the ceramic membrane has a thermal conductivity of 0.020 to 0.080W/m-K.
13. A ceramic membrane according to claim 1, wherein the ceramic membrane has a 5h photodegradation of at least 68% for dyes.
14. The ceramic membrane of claim 13, wherein the dye is methyl orange.
15. A method for the preparation of a ceramic membrane according to any of claims 1 to 14, 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.
16. The method of claim 15, 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.
17. The method of claim 16, wherein the solvent is one, two or more selected from the group consisting of N, N-Dimethylformamide (DMF), ethanol, and water.
18. The method according to claim 17, wherein the solvent is a mixed solvent of ethanol and water.
19. The method according to claim 15 or 16, wherein the mass fraction of the polymeric template is 1 to 16%.
20. The method of claim 16, wherein the rare earth salt is 5 to 22% by mass of the total mass of the spinning dope.
21. The method of any one of claims 15-17, wherein the electrospinning voltage is 10-40kV.
22. As in claimThe method of any one of claims 15 to 17, wherein the electrospinning has a feed rate of 0.2 to 1.8 mL-h -1 。
23. The method of any one of claims 15-17, wherein said electrospinning has a spinning distance of 5-16cm.
24. The method of any one of claims 15-17, wherein the high temperature sintering temperature is 600-1600 ℃.
25. The method of claim 24, wherein the high temperature sintering is performed for a time of 1 to 3 hours.
26. The method of claim 24, wherein the temperature increase rate of the high-temperature sintering is 0.1 to 10 ℃/min.
27. The method of any one of claims 15-16, 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.
28. Use of a ceramic membrane according to any one of claims 1 to 14 and/or a ceramic membrane obtained by a method according to any one of claims 15 to 27 in the field of thermal barrier materials, energy catalysis, radiation protection or uv absorption.
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| 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 |
| 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 |
| CN115838993B (en) * | 2022-12-13 | 2023-09-15 | 南京邮电大学 | High infrared radiation fiber mat and preparation method thereof |
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| CN111592358B (en) * | 2020-04-09 | 2021-08-03 | 中国科学院化学研究所 | Carbide high-entropy ceramic fiber and preparation method thereof |
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