CN109012722B - Cerium dioxide/titanium nitride nanotube taking Ce-MOF as precursor and preparation method and application thereof - Google Patents
Cerium dioxide/titanium nitride nanotube taking Ce-MOF as precursor and preparation method and application thereof Download PDFInfo
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- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000002071 nanotube Substances 0.000 title claims abstract description 38
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 title claims abstract description 35
- 239000002243 precursor Substances 0.000 title claims abstract description 32
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000010936 titanium Substances 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 230000001699 photocatalysis Effects 0.000 claims abstract description 5
- 239000004020 conductor Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- -1 polytetrafluoroethylene Polymers 0.000 claims description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 13
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 13
- 229910052684 Cerium Inorganic materials 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 9
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000003446 ligand Substances 0.000 claims description 9
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 8
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 4
- 239000012018 catalyst precursor Substances 0.000 claims description 4
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 4
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 claims description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- XFTIKWYXFSNCQF-UHFFFAOYSA-N N,N-dipropylformamide Chemical compound CCCN(C=O)CCC XFTIKWYXFSNCQF-UHFFFAOYSA-N 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- WWIKWTYVPCCWSB-UHFFFAOYSA-N cerium(3+) trinitrate heptahydrate Chemical compound O.O.O.O.O.O.O.[N+](=O)([O-])[O-].[Ce+3].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WWIKWTYVPCCWSB-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000011358 absorbing material Substances 0.000 abstract description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012876 carrier material Substances 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000012621 metal-organic framework Substances 0.000 description 22
- 239000000203 mixture Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000011049 filling Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000003795 desorption Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000012695 Ce precursor Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B01J35/39—
-
- B01J35/615—
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- B01J35/647—
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
Abstract
The invention belongs to the technical field of catalyst materials, and discloses a cerium dioxide/titanium nitride nanotube (CeO) taking Ce-MOF as a precursor2TiN NTs) and a preparation method thereof. The cerium dioxide/titanium nitride nanotube is prepared by dissolving a Ce-MOF precursor frame and a titanium source in a solvent, adding the solution into a high-pressure reaction kettle, reacting at 110-200 ℃, cooling, filtering, washing, drying after the reaction is finished, calcining, and performing post-nitridation treatment. The titanium nitride nanotube has regular morphology, larger specific surface area and good electrochemical performance. The method has the advantages of simple equipment requirement, simple and convenient operation, low raw material price and hopeful large-scale production. Can be widely applied to the fields of photocatalysis materials, dielectric and microwave absorbing materials, high-temperature microwave absorbing materials, electrode catalyst carrier materials and heat conducting materials.
Description
Technical Field
The invention belongs to the technical field of catalyst materials, and particularly relates to a cerium dioxide/titanium nitride nanotube (CeO) taking Ce-MOF as a precursor2TiN NTs) and a preparation method and application thereof.
Background
Titanium nitride (TiN) is a cubic crystal, has the characteristics of high hardness, high melting point, high-temperature chemical stability and the like, and is a good electric and heat conductor. Compared with zero-dimensional titanium nitride particles, the hollow and porous one-dimensional titanium nitride nanotubes (TiN NTs) have larger specific surface area, and the mass transfer rate in the reaction process is improved. Due to the interaction between the nanotubes, the conductivity is greatly improved, which is beneficial to the conduction of electrons. There are also reports on the research using titanium nitride nanotubes as carriers. The research of the electrochemical performance of the titanium nitride nanotube as a vanadium battery cathode pair V (II)/V (III) by Zhao Feng Ming et al (Zhao kuming, smelling just, Koliyao, etc.. J. inorganic chemistry report, 2017,33(3):501 and 508.) finds that the titanium nitride has large specific surface area and rapid electronic channel pair V (II)/V (III) shows excellent electrocatalytic activity and reversibility. The research on the catalytic activity and stability of a titanium nitride-carbon nanotube composite carrier supported platinum catalyst [ J ] chemical novel material, 2017(9): 175-.
Metal Organic Frameworks (MOFs) have the advantages of abundant and various structures, high specific surface area, high porosity and the like, and are widely popularized and applied in the fields of gas adsorption, catalysis and the like. CeO (CeO)2Due to its outstanding oxygen storage capacity and redox capacity, it has developed rapidly in the field of environmental catalysis. The performance of the porous catalyst carrier prepared by taking the MOF as the precursor is greatly improved. Patent CN 107824177A introduces CeO taking Ce-MOF as cerium precursor2/TiO2The preparation method of the low-temperature SCR catalyst prepares the catalyst with high catalytic activity for ammonia selective catalytic reduction. Patent CN 106955742A introduces a preparation method and application of a Ce-MOF photocatalytic material, and the Ce-MOF photocatalytic material is successfully prepared, has good optical properties and good thermal stability, and is mild in reaction conditions and free of secondary pollution.
At present, the catalyst prepared by using Ce-MOF as a precursorThe agent being substantially supported on TiO2Or carbon black, and the TiN nano-tube structure is loaded on the carbon black, and no relevant report is found.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the cerium dioxide/titanium nitride nanotube taking Ce-MOF as a precursor is provided.
The invention also aims to provide a preparation method of the cerium dioxide/titanium nitride nanotube taking Ce-MOF as a precursor.
The invention further aims to provide application of the cerium dioxide/titanium nitride nanotube taking Ce-MOF as a precursor.
The purpose of the invention is realized by the following technical scheme:
cerium dioxide/titanium nitride nanotubes (CeO) with Ce-MOF as precursor2the/TiN NTs) is prepared by dissolving a Ce-MOF precursor frame and a titanium source in a solvent, adding the solution into a high-pressure reaction kettle, reacting at 110-200 ℃, cooling, filtering, washing, drying after the reaction is finished, calcining, and performing post-nitridation treatment.
Preferably, the Ce-MOF precursor framework is prepared by dissolving a cerium source and an organic carboxylic acid ligand in an organic solvent, filtering and then drying in vacuum.
More preferably, the cerium source is one or more of cerium acetate, cerium nitrate heptahydrate or cerium nitrate hexahydrate, the organic carboxylic acid ligand is one or more of terephthalic acid, oxalic acid, 2-picolinic acid, malonic acid, trimesic acid or citric acid, the organic solvent is one or more of methanol, ethanol, dimethyl sulfoxide or dipropyl formamide, and the mass ratio of the cerium source to the organic carboxylic acid ligand is (1-10): 1; the volume ratio of the total mass of the cerium source and the organic carboxylic acid ligand to the organic solvent is (0.005-0.050) g:1 mL.
Preferably, the titanium source is more than one of titanyl sulfate, tetraethyl titanate, tetrabutyl titanate or tetrapentyl titanate, and the solvent is absolute ethyl alcohol, butanediol and butyl ether.
Preferably, the volume ratio of the absolute ethyl alcohol, the butanediol and the butyl ether is 2: 1: 1.
preferably, the calcining temperature is 250-550 ℃, and the calcining time is 3-6 h; the temperature of the post-nitridation treatment is 650-800 ℃, and the time of the post-nitridation treatment is 2-5 h.
The preparation method of the cerium dioxide/titanium nitride nanotube with Ce-MOF as the precursor comprises the following specific steps:
s1, dissolving a cerium source and an organic carboxylic acid ligand in an organic solvent, reacting for 1-8 hours at 50-180 ℃, filtering, and drying in a vacuum oven to obtain a Ce-MOF precursor framework;
s2, dissolving a Ce-MOF precursor frame and a titanium source in a solvent, adding the solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and reacting at 110-200 ℃;
s3, after the reaction is finished, cooling, filtering, washing, drying and calcining to obtain a catalyst precursor;
s4, putting the catalyst precursor into a tubular furnace for post-nitridation treatment to obtain the cerium dioxide/titanium nitride nanotube (CeO)2/TiN NTs)。
Preferably, the reaction time in the step S2 is 7-17 h; in the step S3, the drying temperature is 60-100 ℃, and the drying time is 10-16 h.
Preferably, the amount of Ce in the ceria/titanium nitride nanotube in step S4 is 10 to 40 wt%.
The cerium dioxide/titanium nitride nanotube taking Ce-MOF as a precursor is applied to the fields of photocatalytic materials, dielectric and microwave absorbing materials, high-temperature microwave absorbing materials, electrode catalyst carrier materials and heat conducting materials.
Compared with the prior art, the invention has the following beneficial effects:
1. the cerium dioxide/titanium nitride nanotube (CeO) taking Ce-MOF as a precursor2/TiN NTs) has regular morphology, larger specific surface area, higher conductivity and good electrochemical performance.
2. The method of the invention has the advantages of simple equipment requirement, easy operation, safety, low cost and large-scale production.
Drawings
FIG. 1 shows CeO prepared in example 32SEM photograph of/TiN NTs.
FIG. 2 shows CeO prepared in example 32Cyclic voltammograms of/TiN NTs and GC.
FIG. 3 shows CeO prepared in example 42SEM photograph of/TiN NTs.
FIG. 4 shows CeO prepared in example 52XRD spectrum of/TiN NTs.
FIG. 5 shows CeO prepared in example 52SEM photograph of/TiN NTs.
FIG. 6 CeO prepared in example 52the/TiN NTs (a) is a nitrogen adsorption and desorption curve, and (b) is a pore size distribution diagram of the corresponding BJH.
FIG. 7 shows CeO prepared in example 62SEM photograph of/TiN NTs.
Detailed Description
The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
Weighing 0.90g of cerium acetate and 0.75g of terephthalic acid, dissolving in 50mL of methanol, uniformly mixing, adding into a 100mL flask, then placing into an oven, keeping the temperature at 180 ℃ for 8h, cooling to room temperature, taking out, and filtering to obtain a sample. And then drying the sample in a vacuum drying oven for 16h to obtain the Ce-MOF-1 precursor framework.
Example 2
Weighing 1.02g of cerium acetate and 0.88g of adipic acid, dissolving in 100mL of dipropyl formamide, uniformly mixing, adding into a 100mL flask, then placing into an oven, preserving heat at 50 ℃ for 8 hours, cooling to room temperature, taking out, and filtering to obtain a sample. And then drying the sample in a vacuum drying oven for 16h to obtain the Ce-MOF-2 precursor framework.
Example 3
1. The weighed 2.12gCe-MOF-1 precursor frame and 25.62g titanyl sulfate were sequentially added to an autoclave with a polytetrafluoroethylene liner (100mL), followed by 20mL butanediol, 20mL butyl ether and 40mL absolute ethanol, and the reactants were mixed well.
2. Adding the mixture into a polytetrafluoroethylene liner, filling the mixture into a reaction kettle, and reacting for 17 hours at 200 ℃;
3. naturally cooling the reaction kettle to room temperature, filtering, washing with ethanol, and drying in a 60 ℃ oven for 16 h;
4. then placing the mixture in a muffle furnace to calcine the mixture for 5 hours at 250 ℃, and finally calcining the mixture for 5 hours in a tubular furnace at 800 ℃ to obtain CeO2Titanium nitride nanotubes (CeO)2/TiN NTs)。
FIG. 1 shows CeO prepared in this example2SEM photograph of/TiN NTs. As can be seen from FIG. 1, CeO was obtained2the/TiN NTs have the average diameter of 50-200nm and are formed by combining Ce-MOF-1 and titanium nitride nanotubes2TinNTs to give CeO2the/TiN NTs has regular morphology. FIG. 2 shows CeO prepared in this example2Comparison of cyclic voltammetry of/TiN NTs and glassy carbon electrodes. The test conditions were 0.5mol/L H at room temperature2SO4The scanning potential of the solution is-0.2-1.0V (vs. Ag/AgCl), and the scanning speed is 50 mV/s. As can be seen from FIG. 2, after 50 cycles of scanning, no redox peak was present, indicating that CeO was present2the/TiN NTs has good electrochemical performance, and the electrochemical performance of the/TiN NTs is obviously higher than that of a glassy carbon electrode (GC).
Example 4
1. The weighed 2.12gCe-MOF-1 precursor frame and 18.82g titanyl sulfate were sequentially added to an autoclave with a polytetrafluoroethylene liner (100mL), 13mL butanediol, 13mL butyl ether and 26mL absolute ethanol were added, and the reactants were mixed well.
2. Adding the mixture into a polytetrafluoroethylene liner, filling the polytetrafluoroethylene liner into a reaction kettle, and reacting for 16 hours at 200 ℃; naturally cooling the reaction kettle to room temperature, filtering, washing with ethanol, and drying in an oven at 100 deg.C for 16 h;
3. and then placing the titanium nitride nano-tube in a muffle furnace to calcine for 6h at 300 ℃, and finally calcining for 5h in a tube furnace at 800 ℃ to obtain the Ce-MOF-based titanium nitride nano-tube.
FIG. 3 shows CeO prepared in this example2SEM photograph of/TiN NTs. As can be seen from FIG. 3, CeO was obtained2CeO with average diameter of 50-200nm and combined by Ce-MOF-1 and titanium nitride nanotubes2/TiN NTs。
Example 5
1. The weighed 2.12gCe-MOF-2 precursor frame and 25.62g titanyl sulfate were sequentially added to an autoclave with a polytetrafluoroethylene liner (100mL), followed by 14mL butanediol, 14mL butyl ether, and 28mL absolute ethanol, and the reactants were mixed well.
2. Adding the mixture into a polytetrafluoroethylene lining, filling the polytetrafluoroethylene lining into a reaction kettle, and reacting for 16 hours at 110 ℃; and naturally cooling the reaction kettle to room temperature, filtering, washing with ethanol, and drying in an oven at 100 ℃ for 16 h.
4. Then placing the mixture in a muffle furnace to calcine for 5 hours at 550 ℃, and finally calcining for 5 hours in a tubular furnace at 700 ℃ to obtain CeO2/TiN NTs。
FIG. 4 shows CeO prepared in this example2XRD pattern of/TiN NTs. As can be seen from FIG. 4, CeO2The characteristic diffraction peak positions of/TiN NTs show the characteristic diffraction peaks of TiN with face centered cubic structure (fcc) at 36.8 degrees, 42.6 degrees, 61.9 degrees, 74.2 degrees and 77.9 degrees, which shows that the method can prepare TiN with pure face centered cubic structure (fcc). The sample showed cubic CeO at 28.8 °, 33.2 °, 56.2 °, 76.2 °, 80 °2Indicating that the method can prepare CeO2(iii)/TiN NTs. Obtained CeO2SEM of/TiN NTs is shown in FIG. 5, and CeO is obtained2the/TiN NTs have the average diameter of 50-200nm and are formed by combining Ce-MOF-2 and titanium nitride nanotubes2(iii)/TiN NTs. FIG. 6 CeO prepared in this example2the/TiN NTs (a) is a nitrogen adsorption and desorption curve, and (b) is a pore size distribution diagram of the corresponding BJH. As can be seen from FIG. 6, CeO2The nitrogen adsorption and desorption curve of the/TiN NTs is with typical H3Type IV isotherms of the hysteresis rings, illustrating CeO2the/TiN NTs is rich inThe mesopores of (a) exist. FIG. 6 (b) is a BJH pore size distribution curve showing that CeO was present in the sample2the/TiN NTs has more mesopores. Further, CeO can be obtained by calculation using the BET formula2The specific surface area of the/TiN NTs is 148cm2g-1This is mainly due to the large specific surface area of Ce-MOF.
Example 6
1. 2.12gCe-MOF-2 precursor frame and 18.82g titanyl sulfate were weighed into an autoclave with a polytetrafluoroethylene liner (100mL) in sequence, 20mL butanediol, 20mL butyl ether and 40mL absolute ethanol were added, and the reactants were mixed well.
2. Adding the mixture into a polytetrafluoroethylene lining, filling the polytetrafluoroethylene lining into a reaction kettle, and reacting for 17 hours at 200 ℃; and naturally cooling the reaction kettle to room temperature, filtering, washing with ethanol, and drying in an oven at 100 ℃ for 16 h.
5. Then placing the mixture in a muffle furnace to calcine for 6 hours at 500 ℃, and finally calcining for 5 hours in a tubular furnace at 700 ℃ to obtain CeO2/TiN NTs。
Obtained CeO2SEM of/TiN NTs is shown in FIG. 7, and CeO is obtained2The average diameter of the/TiN NTs is 50-200nm, and CeO is formed by combining Ce-MOF-2 and titanium nitride nanotubes2/TiN NTs。
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A preparation method of a cerium dioxide/titanium nitride nanotube taking Ce-MOF as a precursor is characterized by comprising the following specific steps:
s1, dissolving a cerium source and an organic carboxylic acid ligand in an organic solvent, reacting at 50-180 ℃ for 1-8 h, filtering, and drying in a vacuum oven to obtain a Ce-MOF precursor frame;
s2, dissolving the Ce-MOF precursor frame and a titanium source in a solvent, adding the solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and reacting at 110-200 ℃;
s3, after the reaction is finished, cooling, filtering, washing, drying, and calcining at 250-550 ℃ to obtain a catalyst precursor;
and S4, putting the catalyst precursor into a tubular furnace, and performing post-nitridation treatment at 650-800 ℃ to obtain the cerium dioxide/titanium nitride nanotube.
2. The method for preparing cerium dioxide/titanium nitride nanotubes with Ce-MOF as a precursor according to claim 1, wherein the cerium source is one or more of cerium acetate, cerium nitrate heptahydrate or cerium nitrate hexahydrate, the organic carboxylic acid ligand is one or more of terephthalic acid, oxalic acid, 2-picolinic acid, malonic acid, trimesic acid or citric acid, the organic solvent is one or more of methanol, ethanol, dimethyl sulfoxide or dipropyl formamide, and the mass ratio of the cerium source to the organic carboxylic acid ligand is (1-10): 1; the volume ratio of the total mass of the cerium source and the organic carboxylic acid ligand to the organic solvent is (0.005-0.050) g:1 mL.
3. The method for preparing ceria/titanium nitride nanotubes with Ce-MOF as the precursor according to claim 1, wherein the titanium source is one or more of titanyl sulfate, tetraethyl titanate or tetrabutyl titanate in step S2, and the solvent is absolute ethanol, butanediol and butyl ether.
4. The preparation method of the cerium dioxide/titanium nitride nanotube taking Ce-MOF as the precursor according to claim 3, wherein the volume ratio of the absolute ethyl alcohol to the butanediol to the butyl ether is (2-3): 1: 1.
5. the method for preparing the cerium dioxide/titanium nitride nanotube taking Ce-MOF as the precursor according to claim 1, wherein the reaction time in the step S2 is 7-17 h; in the step S3, the drying temperature is 60-100 ℃, and the drying time is 10-16 h.
6. The method for preparing the cerium dioxide/titanium nitride nanotube taking Ce-MOF as the precursor according to claim 1, wherein the calcination time in the step S3 is 3-6 h; the time of the post-nitridation treatment in the step S4 is 2-5 h.
7. The method for preparing cerium dioxide/titanium nitride nanotubes by using Ce-MOF as precursors according to claim 1, wherein the amount of Ce in the cerium dioxide/titanium nitride nanotubes in step S4 is 10-40 wt%.
8. A ceria/titanium nitride nanotube prepared by the method of any one of claims 1 to 7.
9. Use of the ceria/titanium nitride nanotubes of claim 8 in the fields of photocatalytic materials, electrode catalyst support materials and thermally conductive materials.
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