CN109012722A - It is a kind of using Ce-MOF as the ceria of presoma/titanium nitride nano pipe and its preparation method and application - Google Patents
It is a kind of using Ce-MOF as the ceria of presoma/titanium nitride nano pipe and its preparation method and application Download PDFInfo
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- CN109012722A CN109012722A CN201810601404.4A CN201810601404A CN109012722A CN 109012722 A CN109012722 A CN 109012722A CN 201810601404 A CN201810601404 A CN 201810601404A CN 109012722 A CN109012722 A CN 109012722A
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- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 title claims abstract description 51
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001354 calcination Methods 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010936 titanium Substances 0.000 claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000011358 absorbing material Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 229910052684 Cerium Inorganic materials 0.000 claims description 12
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 239000003446 ligand Substances 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 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 8
- 229960000935 dehydrated alcohol Drugs 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
- 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
- 229960004756 ethanol Drugs 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- -1 pentyl ester Chemical class 0.000 claims description 6
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 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
- 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
- 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
- 238000001291 vacuum drying Methods 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
- 239000002071 nanotube Substances 0.000 claims description 3
- SIOXPEMLGUPBBT-UHFFFAOYSA-N Picolinic acid Natural products OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 claims description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- VXKWYPOMXBVZSJ-UHFFFAOYSA-N tetramethyltin Chemical compound C[Sn](C)(C)C VXKWYPOMXBVZSJ-UHFFFAOYSA-N 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 claims 1
- 238000007146 photocatalysis Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000012621 metal-organic framework Substances 0.000 description 21
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000012695 Ce precursor Substances 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 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
- 239000010970 precious metal Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
Classifications
-
- 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—
-
- B01J35/647—
-
- 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
-
- 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 catalyst material technical fields, disclose a kind of using Ce-MOF as the ceria of presoma/titanium nitride nano pipe (CeO2/ TiN NTs) and preparation method thereof.The ceria/titanium nitride nano pipe is that Ce-MOF forerunner's frame and titanium source are dissolved in solvent, and be added in autoclave, it is reacted at 110~200 DEG C, cools down, is filtered, washed, dries after reaction, after calcining, nitrogen treatment is made after progress.The titanium nitride nano pipe has regular pattern and biggish specific surface area, good chemical property.This method equipment requirement is simple, easy to operate, low in raw material price, is expected to be mass produced.It can be widely applied in catalysis material, dielectric and microwave absorbing material, high temperature microwave absorbing material and support materials for electrode catalysts and Heat Conduction Material field.
Description
Technical field
The invention belongs to catalyst material technical fields, more particularly, to a kind of using Ce-MOF as the dioxy of presoma
Change cerium/titanium nitride nano pipe (CeO2/ TiN NTs) and its preparation method and application.
Background technique
Titanium nitride (TiN) is a kind of cubic system crystallization, with spies such as high rigidity, high-melting-point and stability at elevated temperature
Point is good conductive, heat carrier.Relative to the titanium nitride particles of zero dimension, hollow and porous one-dimensional titanium nitride nano pipe
(TiN NTs) has bigger specific surface area, improves the mass transfer rate in reaction process.Due to the phase interaction between nanotube
With electric conductivity obtains larger raising, is conducive to the conduction of electronics.Also have using titanium nitride nano pipe as the research of carrier relevant
Report.(Zhao Fengming, Wen Gang, Kong Liyao wait titanium nitride nano pipe as vanadium battery negative electrode to V (II)/V (III) to Zhao Fengming et al.
Chemical property [J] Chinese Journal of Inorganic Chemistry, 2017,33 (3): 501-508.) the big specific surface area of discovery titanium nitride after research
Excellent electro catalytic activity and invertibity are presented to V (II)/V (III) with quick electron channel.Duan Haonan et al. (Duan Hao
Male, Chen Tao, Liu Jinke wait titanium nitride-carbon nanotube composite carrier load platinum catalyst catalytic activity and stability study
[J] New Chemical Materials, 2017 (9): 175-177.) research after discovery titanium nitride can enhance between precious metals pt and carrier
Interaction, and higher stability and catalytic activity are showed by the catalyst of carrier of TiN-CNTs.
The advantages that metal organic frame (MOFs) is with its rich and varied structure, high-specific surface area, high porosity, in gas
The fields such as absorption, catalysis are widely promoted and applied.CeO2Because of its oxygen storage capacity and redox ability outstanding, in environmental catalysis
Field develops rapidly.It improves a lot in performance by the porous catalyst carrier of precursor preparation of MOF.Patent CN
107824177 A introduce a kind of using Ce-MOF as the CeO of cerium precursor2/TiO2The preparation method of low-temperature SCR catalyst, is prepared
There is the catalyst of high catalytic activity to ammine selectivity catalytic reduction.106955742 A of patent CN describes a kind of Ce-MOF
The preparation method and application of catalysis material is successfully prepared a kind of Ce-MOF catalysis material, has preferable optics special
Property and good thermal stability, reaction condition is mild and does not cause secondary pollution.
Currently, being essentially all to be supported on TiO using the catalyst that Ce-MOF comes out as precursor preparation2Or on carbon black,
Being supported on TiN nano tubular structure yet there are no relevant report.
Summary of the invention
In order to solve above-mentioned the shortcomings of the prior art and disadvantage, provide a kind of using Ce-MOF as the titanium dioxide of presoma
Cerium/titanium nitride nano pipe.
Another object of the present invention is to provide above-mentioned using Ce-MOF as the ceria of presoma/titanium nitride nano pipe
Preparation method.
A further object of the present invention is to provide above-mentioned using Ce-MOF as the ceria of presoma/titanium nitride nano pipe
Using.
The purpose of the present invention is realized by following technical proposals:
It is a kind of using Ce-MOF as the ceria of presoma/titanium nitride nano pipe, the ceria/titanium nitride nano pipe
(CeO2/ TiN NTs) it is that Ce-MOF forerunner's frame and titanium source are dissolved in solvent, and is added in autoclave, 110~
It is reacted at 200 DEG C, cools down, is filtered, washed, dries after reaction, after calcining, nitrogen treatment system after progress
?.
Preferably, Ce-MOF forerunner's frame is to dissolve in cerium source and organic carboxyl acid ligand in organic solvent, mistake
It is made after filter through being dried in vacuo.
It is further preferable that the cerium source is one or more of cerous acetate, seven nitric hydrate ceriums or six nitric hydrate ceriums, institute
State organic carboxyl acid ligand be one of terephthalic acid (TPA), oxalic acid, 2- pyridine carboxylic acid, malonic acid, trimesic acid or citric acid with
On, the organic solvent is one or more of methanol, ethyl alcohol, dimethyl sulfoxide or dipropyl formamide, the cerium source and is had
The mass ratio of the material of machine Carboxylic acid ligand is (1~10): 1；The cerium source and the total quality and organic solvent of organic carboxyl acid ligand
Volume ratio is (0.005~0.050) g:1mL.
Preferably, the titanium source be one of titanyl sulfate, four pentyl ester of tetraethyl titanate, butyl titanate or metatitanic acid with
On, the solvent is dehydrated alcohol, butanediol and butyl ether.
Preferably, the volume ratio of the dehydrated alcohol, butanediol and butyl ether is 2:1:1.
Preferably, the temperature of the calcining is 250~550 DEG C, and the time of the calcining is 3~6h；After described at nitridation
The temperature of reason is 650~800 DEG C, and the time of rear nitrogen treatment is 2~5h.
It is described using Ce-MOF as the ceria of presoma/titanium nitride nano pipe preparation method, including it is following specific
Step:
S1. first cerium source and organic carboxyl acid ligand are dissolved in organic solvent, in 50~180 DEG C of 1~8h of reaction, after filtering
It is dry in vacuum drying oven, obtain Ce-MOF forerunner's frame；
S2. Ce-MOF forerunner's frame, titanium source are dissolved in solvent, and it is anti-to be added to the high pressure with polytetrafluoroethyllining lining
It answers in kettle, is reacted at 110~200 DEG C；
S3. it cools down, be filtered, washed, dry after reaction, obtain catalyst precarsor after calcining；
S4. catalyst precarsor is put into after tube furnace carries out nitrogen treatment to get to ceria/titanium nitride nano pipe again
(CeO2/TiN NTs)。
Preferably, the time of reaction described in step S2 is 7~17h；Dry temperature described in step S3 is 60~100
DEG C, the time of the drying is 10~16h.
Preferably, the amount of Ce is 10~40wt% in ceria described in step S4/titanium nitride nano pipe.
Described is the ceria of presoma/titanium nitride nano pipe in catalysis material, dielectric and microwave using Ce-MOF
Application in absorbing material, high temperature microwave absorbing material and support materials for electrode catalysts and Heat Conduction Material field.
Compared with prior art, the invention has the following advantages:
1. of the invention using Ce-MOF as the ceria of presoma/titanium nitride nano pipe (CeO2/ TiN NTs) there are rule
Whole pattern and biggish specific surface area, higher electric conductivity, while there is good chemical property.
2. equipment requirement needed for method of the invention is simple and operation is easy, safety, while at low cost, can give birth on a large scale
It produces.
Detailed description of the invention
Fig. 1 is the CeO prepared in embodiment 32The SEM photograph of/TiN NTs.
Fig. 2 is CeO prepared by embodiment 32The cyclic voltammetric comparison diagram of/TiN NTs and GC.
Fig. 3 is the CeO prepared in embodiment 42The SEM photograph of/TiN NTs.
Fig. 4 is CeO prepared by embodiment 52The XRD spectra of/TiN NTs.
Fig. 5 is the CeO prepared in embodiment 52The SEM photograph of/TiN NTs.
The CeO prepared in Fig. 6 embodiment 52/ TiN NTs (a) is nitrogen adsorption desorption curve, (b) is its corresponding BJH
Graph of pore diameter distribution.
Fig. 7 is the CeO prepared in embodiment 62The SEM photograph of/TiN NTs.
Specific embodiment
The contents of the present invention are further illustrated combined with specific embodiments below, but should not be construed as limiting the invention.
Unless otherwise specified, the conventional means that technological means used in embodiment is well known to those skilled in the art.Except non-specifically
Illustrate, reagent that the present invention uses, method and apparatus is the art conventional reagents, method and apparatus.
Embodiment 1
Cerous acetate 0.90g is weighed, terephthalic acid (TPA) 0.75g is dissolved in 50mL methanol, and one is added after mixing
It in the flask of 100mL, is then placed in baking oven, in 180 DEG C of heat preservation 8h, is cooled to room temperature taking-up and sample is obtained by filtration.Later will
Sample dries 16h in a vacuum drying oven, and Ce-MOF-1 forerunner's frame can be obtained.
Embodiment 2
Cerous acetate 1.02g is weighed, adipic acid 0.88g is dissolved in 100mL dipropyl formamide, one is added after mixing
It in the flask of a 100mL, is then placed in baking oven, in 50 DEG C of heat preservation 8h, is cooled to room temperature taking-up and sample is obtained by filtration.Later will
Sample dries 16h in a vacuum drying oven, and Ce-MOF-2 forerunner's frame can be obtained.
Embodiment 3
1. sequentially adding weighed 2.12gCe-MOF-1 forerunner's frame and 25.62g titanyl sulfate with polytetrafluoroethylene (PTFE)
In the autoclave of liner (100mL), 20mL butanediol, 20mL butyl ether and 40mL dehydrated alcohol are added, reactant is mixed equal
It is even.
2. said mixture joined polytetrafluoroethyllining lining to put into reaction kettle, 17h is reacted at 200 DEG C；
3. naturally cooling to room temperature to reaction kettle, then filter, using ethanol washing, then is placed in 60 DEG C of baking ovens, it is dry
Time 16h；
4. being placed in Muffle furnace again in 250 DEG C of calcining 5h, finally 800 DEG C of calcining 5h in tube furnace, obtain CeO2/ nitridation
Titanium nanotube (CeO2/TiN NTs)。
Fig. 1 is the CeO prepared in the present embodiment2The SEM photograph of/TiN NTs.From figure 1 it appears that gained CeO2/
TiN NTs average diameter is in 50~200nm, the CeO being composed of Ce-MOF-1 and titanium nitride nano pipe2/ TiN NTs, obtains
To CeO2/ TiN NTs has regular pattern.Fig. 2 is CeO manufactured in the present embodiment2The circulation of/TiN NTs and glass-carbon electrode volt
Pacify comparison diagram.Test condition is at room temperature in the H of 0.5mol/L2SO4Solution, scanning current potential are -0.2~1.0V (vs.Ag/
AgCl), sweep speed 50mV/s.As can be known from Fig. 2, after 50 circle scannings, the presence of redox peaks is had no, is shown
CeO2/ TiN NTs has good chemical property, and its chemical property is apparently higher than glass-carbon electrode (GC).
Embodiment 4
1. sequentially adding weighed 2.12gCe-MOF-1 forerunner's frame and 18.82g titanyl sulfate with polytetrafluoroethylene (PTFE)
In the autoclave of liner (100mL), 13mL butanediol, 13mL butyl ether and 26mL dehydrated alcohol are added, reactant is mixed equal
It is even.
2. polytetrafluoroethyllining lining is added in said mixture to put into reaction kettle, 16h is reacted at 200 DEG C；Wait react
Kettle naturally cools to room temperature, then filters, and using ethanol washing, then is placed in 100 DEG C of baking ovens, drying time 16h；
3. being placed in Muffle furnace again in 300 DEG C of calcining 6h, finally 800 DEG C of calcining 5h in tube furnace, obtain based on Ce-
The titanium nitride nano pipe of MOF.
Fig. 3 is the CeO prepared in the present embodiment2The SEM photograph of/TiN NTs.From figure 3, it can be seen that gained CeO2/
The average diameter of TiN NTs is in 50-200nm, the CeO being composed of Ce-MOF-1 and titanium nitride nano pipe2/TiN NTs。
Embodiment 5
1. sequentially adding weighed 2.12gCe-MOF-2 forerunner's frame and 25.62g titanyl sulfate with polytetrafluoroethylene (PTFE)
In the autoclave of liner (100mL), 14mL butanediol, 14mL butyl ether and 28mL dehydrated alcohol are added, reactant is mixed equal
It is even.
2. said mixture is added polytetrafluoroethyllining lining and puts into reaction kettle, 16h is reacted at 110 DEG C；Wait react
Kettle naturally cools to room temperature, then filters, and using ethanol washing, then is placed in 100 DEG C of baking ovens, drying time 16h.
4. being placed in 550 DEG C of calcining 5h in Muffle furnace again, finally 700 DEG C of calcining 5h in tube furnace, obtain CeO2/TiN
NTs。
Fig. 4 is CeO prepared by the present embodiment2The XRD diagram of/TiN NTs.As can be known from Fig. 4, CeO2The spy of/TiN NTs
There is the spy of the TiN of face-centred cubic structure (fcc) in 36.8 °, 42.6 °, 61.9 °, 74.2 °, 77.9 ° respectively in sign diffraction maximum position
Diffraction maximum is levied, this shows that this method can prepare the TiN of pure phase face-centred cubic structure (fcc).Sample 28.8 °, 33.2 °,
56.2 °, 76.2 °, 80 ° there is cuboidal CeO2Characteristic diffraction peak, this shows that this method can prepare CeO2/TiN
NTs.Gained CeO2The SEM of/TiN NTs is as shown in figure 5, gained CeO2/ TiN NTs average diameter is in 50~200nm, by Ce-
The CeO that MOF-2 and titanium nitride nano pipe are composed2/TiN NTs.The CeO prepared in Fig. 6 the present embodiment2/ TiN NTs (a) is
Nitrogen adsorption desorption curve, (b) graph of pore diameter distribution for being its corresponding BJH.It will be appreciated from fig. 6 that CeO2The nitrogen of/TiN NTs is inhaled
Attached desorption curve is with typical case H3IV type thermoisopleth of hysteresis loop, illustrates CeO2/ TiN NTs has mesoporous presence abundant.Figure
(b) is BJH pore size distribution curve in 6, it is known that sample CeO2There are more mesoporous by/TiN NTs.In addition, passing through BET formula meter
Calculation can obtain CeO2The specific surface area of/TiN NTs is 148cm2g-1, this is mainly due to Ce-MOF with biggish specific surface area.
Embodiment 6
1. 2.12gCe-MOF-2 forerunner's frame will be weighed and 18.82g titanyl sulfate is sequentially added in polytetrafluoroethylene (PTFE)
In the autoclave for serving as a contrast (100mL), 20mL butanediol, 20mL butyl ether and 40mL dehydrated alcohol are added, reactant is uniformly mixed.
2. polytetrafluoroethyllining lining is added in said mixture to put into reaction kettle, 17h is reacted at 200 DEG C；Wait react
Kettle naturally cools to room temperature, then filters, and using ethanol washing, then is placed in 100 DEG C of baking ovens, drying time 16h.
5. being placed in 500 DEG C of calcining 6h in Muffle furnace again, finally 700 DEG C of calcining 5h in tube furnace, obtain CeO2/TiN
NTs。
Gained CeO2The SEM of/TiN NTs is as shown in fig. 7, gained CeO2The average diameter of/TiN NTs in 50~200nm,
The CeO that Ce-MOF-2 and titanium nitride nano pipe are composed2/TiN NTs。
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by change, modification, substitution, combination and simplify,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of using Ce-MOF as the ceria of presoma/titanium nitride nano pipe, which is characterized in that the ceria/nitrogen
Changing titanium nanotube is that Ce-MOF forerunner's frame and titanium source are dissolved in solvent, and is added in autoclave, 110~200
It is reacted at DEG C, cools down, is filtered, washed, dries after reaction, after calcining, nitrogen treatment is made after progress.
2. according to claim 1 using Ce-MOF as the ceria of presoma/titanium nitride nano pipe, which is characterized in that
Ce-MOF forerunner's frame is to dissolve in cerium source and organic carboxyl acid ligand in organic solvent, is made after filtering through vacuum drying
?.
3. according to claim 2 using Ce-MOF as the ceria of presoma/titanium nitride nano pipe, which is characterized in that
The cerium source is one or more of cerous acetate, seven nitric hydrate ceriums or six nitric hydrate ceriums, and the organic carboxyl acid ligand is pair
One or more of phthalic acid, oxalic acid, 2- pyridine carboxylic acid, malonic acid, trimesic acid or citric acid, the organic solvent are first
The amount of the substance of one or more of alcohol, ethyl alcohol, dimethyl sulfoxide or dipropyl formamide, the cerium source and organic carboxyl acid ligand
Than for (1~10): 1；The volume ratio of the cerium source and the total quality and organic solvent of organic carboxyl acid ligand be (0.005~
0.050) g:1mL.
4. according to claim 1 using Ce-MOF as the ceria of presoma/titanium nitride nano pipe, which is characterized in that
The titanium source is one or more of titanyl sulfate, four pentyl ester of tetraethyl titanate, butyl titanate or metatitanic acid, and the solvent is nothing
Water-ethanol, butanediol and butyl ether.
5. according to claim 4 using Ce-MOF as the ceria of presoma/titanium nitride nano pipe, which is characterized in that
The volume ratio of the dehydrated alcohol, butanediol and butyl ether is (2~3): 1:1.
6. according to claim 1 using Ce-MOF as the ceria of presoma/titanium nitride nano pipe, which is characterized in that
The temperature of the calcining is 250~550 DEG C, and the time of the calcining is 3~6h；It is described after nitrogen treatment temperature be 650~
800 DEG C, the time of rear nitrogen treatment is 2~5h.
7. according to claim 1-6 using Ce-MOF as the ceria of presoma/titanium nitride nano pipe system
Preparation Method, which is characterized in that comprise the following specific steps that:
S1. first cerium source and organic carboxyl acid ligand are dissolved in organic solvent, in 50~180 DEG C of 1~8h of reaction, in true after filtering
It is dry in empty baking oven, obtain Ce-MOF forerunner's frame；
S2. Ce-MOF forerunner's frame, titanium source are dissolved in solvent, and are added to the autoclave with polytetrafluoroethyllining lining
In, it is reacted at 110~200 DEG C；
S3. it cools down, be filtered, washed, dry after reaction, obtain catalyst precarsor after calcining；
S4. catalyst precarsor is put into after tube furnace carries out nitrogen treatment to get to ceria/titanium nitride nano pipe again.
8. it is according to claim 7 using Ce-MOF as the ceria of presoma/titanium nitride nano pipe preparation method,
It is characterized in that, the time of reaction described in step S2 is 7~17h；Dry temperature described in step S3 is 60~100 DEG C, institute
Stating the dry time is 10~16h.
9. it is according to claim 7 using Ce-MOF as the ceria of presoma/titanium nitride nano pipe preparation method,
It is characterized in that, the amount of Ce is 10~40wt% in ceria described in step S4/titanium nitride nano pipe.
It using Ce-MOF is the ceria of presoma/titanium nitride nano pipe in photocatalysis 10. described in any one of claims 1-6
In material, dielectric and microwave absorbing material, high temperature microwave absorbing material and support materials for electrode catalysts and Heat Conduction Material field
Application.
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