CN108325553A - A kind of preparation method with the titanium nitride microspherical catalyst for coating core structure - Google Patents
A kind of preparation method with the titanium nitride microspherical catalyst for coating core structure Download PDFInfo
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- CN108325553A CN108325553A CN201810104308.9A CN201810104308A CN108325553A CN 108325553 A CN108325553 A CN 108325553A CN 201810104308 A CN201810104308 A CN 201810104308A CN 108325553 A CN108325553 A CN 108325553A
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- preparation
- titanium nitride
- core structure
- pvp
- microspherical catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000011248 coating agent Substances 0.000 title claims abstract description 18
- 238000000576 coating method Methods 0.000 title claims abstract description 18
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 156
- 239000000243 solution Substances 0.000 claims description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000010792 warming Methods 0.000 claims description 15
- 229960005196 titanium dioxide Drugs 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000003595 mist Substances 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- NJIQKCISLWVESA-UHFFFAOYSA-J [Ti](Cl)(Cl)(Cl)Cl.C(CCC)N1CN(C=C1)C Chemical class [Ti](Cl)(Cl)(Cl)Cl.C(CCC)N1CN(C=C1)C NJIQKCISLWVESA-UHFFFAOYSA-J 0.000 claims description 3
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 235000013772 propylene glycol Nutrition 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims 2
- 239000011259 mixed solution Substances 0.000 claims 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 230000017105 transposition Effects 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 23
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 17
- 230000007062 hydrolysis Effects 0.000 abstract description 13
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000007788 liquid Substances 0.000 abstract description 5
- 239000010953 base metal Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 238000007885 magnetic separation Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 38
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 19
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 19
- 229910021529 ammonia Inorganic materials 0.000 description 16
- 238000005253 cladding Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 8
- 229910000085 borane Inorganic materials 0.000 description 7
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 7
- 230000004913 activation Effects 0.000 description 6
- 235000013339 cereals Nutrition 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 5
- 238000005406 washing Methods 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 235000011054 acetic acid Nutrition 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical class CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 1
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 1
- UGDAWAQEKLURQI-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethanol;hydrate Chemical compound O.OCCOCCO UGDAWAQEKLURQI-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910003203 NH3BH3 Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- -1 start timing Substances 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
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- Thermal Sciences (AREA)
- Dispersion Chemistry (AREA)
- Catalysts (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The step of the step of the step of a kind of preparation method with the titanium nitride microspherical catalyst for coating core structure includes the steps that mainly the homogeneous liquid preparations of PVP, the preparation of high dispersive iron oxide microballoon, titania precursor body are prepared and coated and the nitridation of titanium oxide coating.The present invention be directed to the Track characters that ammonia borane hydrolysis releases hydrogen reaction, one kind is provided using base metal as raw material, production cost is low, large specific surface area, catalytic activity is higher, ammonia borane hydrolysis reaction rate can be adjusted, and the preparation method of magnetic separation recovery and the non-noble metal-based catalysts recycled can be carried out, effectively reduce production and application cost.
Description
Technical field
The present invention relates to catalyst preparation technical field, specifically a kind of titanium nitride with cladding core structure is micro-
The preparation method of sphere catalyst, the catalytic water which is primarily adapted for use in hydrogen storage material ammonia borine explain hydrogen.
Background technology
The theoretical hydrogen of ammonia borine (Ammonia Borane, abbreviation AB) is up to 19.6wt.%, is to be found so far
The highest hydride type hydrogen storage material of hydrogen content.AB is stable white crystal at normal temperatures and pressures, non-volatile, non-toxic,
Thermal stability is stronger, water-soluble and certain organic solvents.By means of suitable catalyst, AB can be controllable by modes such as hydrolysis
Ground discharges hydrogen：NH3BH3 + 2H2O = NH4 + +BO2 - + 3H2.Hydrolysis releases the rate control of hydrogen, with used catalyst
Pattern, phase, size and mode of loading it is closely related.Therefore, it is the premise for realizing AB application developments to seek effective catalyst
The basis and.Existing catalyst research, in terms of being mostly focused on the noble metals such as Pt, Pd and Rh, the catalytic effect of these catalyst
Preferably, but it is at high price, it is to restrict its major obstacle promoted and applied.It is that basic the novel of active constituent is urged to carry out base metal
The preparation and application of agent are studied, and have very important theory significance and application value.
Invention content
The purpose of the present invention is：The Track character that hydrogen reaction is released for ammonia borane hydrolysis, provide one kind is with base metal
Raw material, production cost is low, and large specific surface area, catalytic activity is higher, ammonia borane hydrolysis reaction rate can be adjusted, and can
The preparation method of magnetic separation recovery and the non-noble metal-based catalysts recycled is carried out, effectively reduces production and application cost.
In order to solve the above technical problems, the technical solution adopted by the present invention is：A kind of nitridation with cladding core structure
The preparation method of titanium microspherical catalyst, mainly includes the following steps that：
Step 1：The preparation of the homogeneous liquid of PVP：Under room temperature, it is 8 according to the volume ratio of polyalcohol and water:The ratio of (1 ~ 3)
Example is made into 200ml alcohol water mixed solvents, and polyvinylpyrrolidone is added（PVP）4 ~ 10 g, ultrasonic disperse handle 30 ~ 60min,
Obtain PVP homogeneous phase solutions；
Step 2：The preparation of high dispersive iron oxide microballoon：Sodium hydroxide is added in the PVP homogeneous phase solution 100ml for taking step 1 to prepare
（NaOH）0.8 ~ 2.0g, stirring to dissolving；Then 0.01 ~ 0.06 mol of soluble ferric iron salt is added, is warming up to 40 ~ 80 DEG C, continues
Brown color is presented in stirring, 30 ~ 60min of reaction, solution；Brown yellow solution is moved into autoclave, charging is than being 80%, 180
5 ~ 8h is reacted at ~ 220 DEG C, reaction terminates, and is cooled to room temperature, centrifuges, with absolute ethyl alcohol and water alternately washing 3 ~ 5 times；Separation
The solid gone out is dried in vacuo 3 ~ 5h at 40 ~ 60 DEG C, obtains iron oxide microballoon, and vacuum is protected dry spare；
Step 3：The preparation of titania precursor body and cladding：The another PVP homogeneous phase solutions taken obtained by 100ml step 1, in room temperature
Under the conditions of, 0.5 ~ 0.9mol organic acids are added, ultrasonic disperse handles 20 ~ 40min, adds 0.05 ~ 0.1 mol of titanate esters, after
It is continuous to be ultrasonically treated, until solution becomes yellow transparent colloidal；Then, iron oxide 0.5 ~ 1.2g of microballoon obtained by step 2 is added,
Stirring is warming up to 50 ~ 70 DEG C, slow evaporation, until solvent is evaporated；It takes out gel and is evaporated object, at 600 ~ 800 DEG C at high temperature
2 ~ 4h is managed, titanium-oxide-coated magnetic core micro mist is obtained；
Step 4：The nitridation of titanium oxide coating：The obtained titanium oxide fine powder product of step 3 is placed in tube-type atmosphere furnace, is taken out
After vacuum, 400 ~ 500 DEG C are warming up to 5 ~ 10 DEG C of speed per minute, 1 ~ 2 h is kept the temperature, then passes to ammonia（NH3）, control NH3
Flow velocity be 150 ~ 180 mlmin-1, continue to be warming up to 650 ~ 750 DEG C with 5 ~ 10 DEG C per minute, 2 ~ 4h of heat preservation at a temperature of this,
Ammonia is converted into 80 ~ 120 mlmin later-1The nitrogen of flow velocity stops heating, is cooled to room temperature naturally, you can obtains grey black
The titanium nitride microspherical catalyst with cladding core structure of color.
Further, in the step 1, it is ethylene glycol, diethylene glycol (DEG) and α-to prepare the polyalcohol used in alcohol water mixed solvent
Any one in propylene glycol.
Further, in the step 1, the model K30 of polyvinylpyrrolidone, molecular weight Mw=1 × 104。
Further, in the step 2, soluble ferric iron salt is four chlorination of ferric acetyl acetonade or 1- butyl -3- methylimidazoles
Iron（[BMIM]FeCl4）.
Further, in the step 3, organic acid refers to any one in acetic acid, citric acid and lactic acid.
Further, in the step 3, titanate esters refer in butyl titanate, tetraisopropyl titanate and tetraethyl titanate
Any one.
Further, the described ultrasonic disperse processing, to select power be 240w, the supersonic generator that frequency is 40kHz.
Beneficial effects of the present invention：
1, a kind of preparation method with the titanium nitride microspherical catalyst for coating core structure of the invention, selection base metal are
Raw material, cheap and easy to get, cost is relatively low, and preparation condition is milder, and technical process is simple, easily controllable, and in preparation process
There is no environmental pollution.
2, the hydrothermal synthesis reaction that the present invention is assisted by auxiliary agent, has been prepared that dispersion degree is high, ball-type is regular, grain size is equal
Even iron oxide micron particles；And in this, as carrier, approach is nitrogenized by collosol and gel cladding, high-temperature process and ammonia, is made
Thin layer of titanium nitride is uniformly adhered to iron oxide microsphere surface, and the catalyst microspheres generated still keep certain magnetism（See attached
Fig. 2）, thus be easy to use during magnetic separation separation, recycle and recycle, contribute to reduce catalyst use cost.
Meanwhile the degree of scatter of catalyst, and then the rate of controllable catalytic hydrolysis reaction can be adjusted by magnetic control means.
3, heating rate, residence time and NH when the present invention is nitrogenized by Reasonable Regulation And Control titanium oxide3Flow velocity, make
Microporous open structure is presented in the thin layer of titanium nitride formed after nitridation（See attached drawing 1）, thus thus obtained microsphere catalyst specific surface
Product is larger.According to surveying and determination, the average apparent grain size of the catalyst is 1.20 μm, and average specific surface area is 37.4 m2·g-1。
4, nitrogen is inserted into Titanium intracell by the present invention by nitrogenizing, and so that the d bands hole of Titanium is increased, is taken
Rice energy level lowers, thus causes the surface nature of TiN clads and catalytic performance similar with platinum-group noble metals, not only electric conductivity
It is good preferable and corrosion-resistant, physicochemical stability is high.It measures according to the experiment, which is used for the ammonia boron of 0.5wt.% at 25 DEG C
Alkane（AB）Hydrolysis release hydrogen, averagely release hydrogen rate be 8695.8 mlmin-1·g-1, release the average apparent activation of hydrogen reaction
Can be 39.99 kJmol-1。
Description of the drawings
Fig. 1 is the titanium nitride microspherical catalyst amplification 10000 with cladding core structure obtained by the embodiment of the present invention 1
SEM photograph again；
Fig. 2 is to have the magnetic of the titanium nitride microspherical catalyst of cladding core structure in the solution obtained by the embodiment of the present invention 1
Property characterization photo（Right side is magnet in figure）；
Fig. 3 is to release hydrogen volume at any time when using 1 made catalyst of embodiment to carry out ammonia borine catalyzing hydrolysis at different temperatures
Between change curve；
Fig. 4 is the rate constants k for using 1 made catalyst of embodiment to carry out ammonia borine catalytic hydrolysis reaction at different temperatures
Variation relation figure between logarithm (lnk) and the inverse (1/T) of temperature T.
Specific implementation mode
The following is specific embodiments of the present invention, and embodiment below facilitates a better understanding of the present invention, but does not limit
The present invention.The experimental implementation process is not indicating it is to carry out at normal temperatures and pressures.
Embodiment 1
A kind of preparation method with the titanium nitride microspherical catalyst for coating core structure, includes the following steps：
Step 1：At room temperature, according to the volume ratio of glycol/water 8:1 ratio prepares 200ml mixed solvents, and PVP is added
4g, ultrasonic disperse 30min obtain PVP homogeneous phase solutions；100ml PVP homogeneous phase solutions are taken, NaOH 0.8g are added, are stirred to molten
Solution；Then ferric acetyl acetonade 0.01mol is added, is warming up to 40 DEG C, continues stirring, 30 min of reaction, brown color is presented in solution；It will
80ml brown yellow solutions move into the autoclave of 100ml volumes, and 5h is reacted at 180 DEG C, and reaction terminates, and is cooled to room temperature,
It centrifuges, with absolute ethyl alcohol and water alternately washing 3 times；The solid isolated is dried in vacuo 3 h at 40 DEG C, and it is micro- to obtain iron oxide
Ball, vacuum are protected dry spare；
Step 2：Under room temperature, 100ml PVP homogeneous phase solutions are taken, 0.5 mol acetic acid, ultrasonic disperse 20min are added, then add
Enter 0.05 mol of butyl titanate, continue to be ultrasonically treated, until solution becomes yellow transparent colloidal；Then, iron oxide is added
Microballoon 0.5g, stirring are warming up to 50 DEG C, slow evaporation, until solvent is evaporated；It takes out gel and is evaporated object, the high temperature at 600 DEG C
2 h are handled, titanium-oxide-coated magnetic core micro mist is obtained；
Step 3：Titanium-oxide-coated magnetic core micro mist is placed in tube-type atmosphere furnace, is first vacuumized, is then heated up with 5 DEG C per minute
To 400 DEG C, 1h is kept the temperature, ammonia is then passed to（NH3）, control NH3Flow velocity is 150 mlmin-1, continue to rise with 5 DEG C per minute
Temperature keeps the temperature 2 h at this temperature to 650 DEG C, and ammonia is converted to 80 mlmin later-1The nitrogen of flow velocity stops heating, from
So it is cooled to room temperature, you can obtain the titanium nitride microspherical catalyst with cladding core structure of black gray expandable.
According to surveying and determination, the average grain diameter of the catalyst is 860nm, and average specific surface area is 40.7 m2·g-1, catalyst is existed
The ammonia borine of 0.5wt.% is used at 25 DEG C（AB）Hydrolysis release hydrogen, averagely release hydrogen rate be 8498.3 mlmin-1·g-1,
The average apparent activation for releasing hydrogen reaction is 39.92 kJmol-1。
Embodiment 2
A kind of preparation method with the titanium nitride microspherical catalyst for coating core structure, includes the following steps：
Step 1：At room temperature, according to the volume ratio 8 of diethylene glycol (DEG)/water:3 ratio prepares 200ml mixed solvents, and PVP is added
10g, ultrasonic disperse 60min obtain PVP homogeneous phase solutions；100ml PVP homogeneous phase solutions are taken, NaOH 2.0g are added, are stirred to molten
Solution；Then 1- butyl -3- methylimidazole titanium tetrachloride 0.06mol are added, are warming up to 80 DEG C, continues stirring, react 60 min, it is molten
Brown color is presented in liquid；80ml brown yellow solutions are moved into the autoclave of 100ml volumes, 8h is reacted at 220 DEG C, reacted
Terminate, be cooled to room temperature, centrifuge, with absolute ethyl alcohol and water alternately washing 5 times；The solid isolated is dried in vacuo 5 at 60 DEG C
H, obtains iron oxide microballoon, and vacuum is protected dry spare；
Step 2：Under room temperature, it takes 100ml PVP homogeneous phase solutions, is added 0.9 mol citric acids, ultrasonic disperse 40min, then
0.1 mol of tetraisopropyl titanate is added, continues to be ultrasonically treated, until solution becomes yellow transparent colloidal；Then, oxidation is added
Iron microballoon 1.2g, stirring are warming up to 70 DEG C, slow evaporation, until solvent is evaporated；It takes out gel and is evaporated object, it is high at 800 DEG C
Temperature 4 h of processing, obtain titanium-oxide-coated magnetic core micro mist；
Step 3：Titanium-oxide-coated magnetic core micro mist is placed in tube-type atmosphere furnace, is first vacuumized, is then heated up with 10 DEG C per minute
To 500 DEG C, 2 h are kept the temperature, ammonia is then passed to（NH3）, control NH3Flow velocity is 180 mlmin-1, continue with 10 DEG C per minute
750 DEG C are warming up to, keeps the temperature 4h at this temperature, ammonia is converted into 120 mlmin later-1The nitrogen of flow velocity stops heating,
Naturally it is cooled to room temperature, you can obtain the titanium nitride microspherical catalyst with cladding core structure of black gray expandable.
According to surveying and determination, the average grain diameter of the catalyst is 1270nm, and average specific surface area is 36.8 m2·g-1, by catalyst
The ammonia borine of 0.5wt.% is used at 25 DEG C（AB）Hydrolysis release hydrogen, averagely release hydrogen rate be 9126.7 mlmin-1·g-1, the average apparent activation for releasing hydrogen reaction is 38.76kJmol-1。
Embodiment 3
A kind of preparation method with the titanium nitride microspherical catalyst for coating core structure, includes the following steps：
Step 1：At room temperature, according to the volume ratio 8 of α-propylene glycol/water:2 ratio prepares 200ml mixed solvents, and PVP is added
7g, ultrasonic disperse 45min obtain PVP homogeneous phase solutions；100ml PVP homogeneous phase solutions are taken, NaOH 1.4g are added, are stirred to molten
Solution；Then 1- butyl -3- methylimidazole titanium tetrachloride 0.03mol are added, are warming up to 60 DEG C, continues stirring, react 45 min, it is molten
Brown color is presented in liquid；80ml brown yellow solutions are moved into the autoclave of 100ml volumes, 6.5h is reacted at 200 DEG C, instead
It should terminate, be cooled to room temperature, centrifuge, with absolute ethyl alcohol and water alternately washing 4 times；The solid isolated is dried in vacuo at 50 DEG C
4 h, obtain iron oxide microballoon, and vacuum is protected dry spare；
Step 2：Under room temperature, 100ml PVP homogeneous phase solutions are taken, 0.7 mol lactic acid, ultrasonic disperse 30min are added, then add
Enter 0.07 mol of tetraethyl titanate, continue to be ultrasonically treated, until solution becomes yellow transparent colloidal；Then, iron oxide is added
Microballoon 0.85g, stirring are warming up to 60 DEG C, slow evaporation, until solvent is evaporated；It takes out gel and is evaporated object, it is high at 700 DEG C
Temperature 3 h of processing, obtain titanium-oxide-coated magnetic core micro mist；
Step 3：Titanium-oxide-coated magnetic core micro mist is placed in tube-type atmosphere furnace, is first vacuumized, is then heated up with 7 DEG C per minute
To 450 DEG C, 1.5h is kept the temperature, ammonia is then passed to（NH3）, control NH3Flow velocity is 165 mlmin-1, continue with 7 DEG C per minute
700 DEG C are warming up to, keeps the temperature 3 h at this temperature, ammonia is converted into 100 mlmin later-1The nitrogen of flow velocity stops adding
Heat is slowly cooled to room temperature, you can obtains the titanium nitride microspherical catalyst with cladding core structure of black gray expandable.
According to surveying and determination, the average grain diameter of the catalyst is 710nm, and average specific surface area is 39.8 m2·g-1, catalyst is existed
The ammonia borine of 0.5wt.% is used at 25 DEG C（AB）Hydrolysis release hydrogen, averagely release hydrogen rate be 9088.4 mlmin-1·g-1,
The average apparent activation for releasing hydrogen reaction is 41.03 kJmol-1。
Urging for AB has been carried out to the titanium nitride microspherical catalyst with cladding core structure obtained by the embodiment of the present invention 1
Change hydrolysis ice thaw characteristics research, specific experiment method and result are as follows：
Experimental method：It selects volume heavy wall glass bomb appropriate as reactor, is placed in transparent glass constant temperature water bath,
Reaction solution is implemented to stir using hermetically sealed underwater magnetic stirring apparatus, the soft stagnant gas of mineral wool is equipped in pressure bottle upper end outlet
Layer, then connect with vertical efficient condenser pipe, it is condensed with 0 DEG C of deep cooling recirculated water；Derived gas, which is passed through, after condensed is placed in
The gas trapping trap of ice-water bath, trap is interior later to lead gas to imurity-removal gas equipped with enough anhydrous solid calcium chloride
Enter to drain gas collection proportioning device, to collect, to measure hydrogen output in due course.It is 25 ± 0.2 DEG C that precision, which is arranged, in bath temperature, will
Reactor is added in the AB aqueous solutions of a concentration of 0.5wt.% of 10 ml, adds the 1 gained titanium nitride microballoon of embodiment of certain mass
As catalyst, start timing, and hydrogen volume is released in time recording AB hydrolytic processes.Based on same principle and method, change
The hydrogen volume of releasing under different temperatures can be obtained in hydrolysis temperature, accordingly, can calculate table according to the experimental data under different temperatures
See activation energy.Acquired results are tested, are compiled in Fig. 3 together.
, it is apparent that 1 gained catalyst of embodiment is in the microspheroidal of comparison rule from Fig. 1, surface porosity is covered with
Micropore, grain size is between 0.8 ~ 1.4 μm.
It is found from Fig. 2, the fine solid particles in vial of liquid are adsorbed in bottle wall, are shown obtained by the present invention
Catalyst granules have stronger magnetism, can be attracted by bottle external magnet.
Fig. 3 shows：It is catalyzed using the made catalyst of the present invention, under the conditions of four different hydrolysis temperatures, experience is not
Volume with hydrogen produced by the reaction time is different, and the temperature the high more is conducive to be promoted and releases hydrogen rate, but is reacted to
When 8min, maximum hydrogen output can reach at four temperature.
In Fig. 4, the rate constants k of 1 gained catalyst ammonia borane hydrolysis of embodiment under different temperatures reaction
Logarithm (lnk) and the inverse (1/T) of temperature T are mapped, it is not difficult to find that showing linear well close between four data points
System, it is possible thereby to determine the apparent activation energy Ea of reaction.
Claims (7)
1. a kind of preparation method with the titanium nitride microspherical catalyst for coating core structure, which is characterized in that including following step
Suddenly：
Step 1: the preparation of PVP homogeneous phase solutions
At room temperature, it is 8 according to the volume ratio of polyalcohol and water:The ratio of (1 ~ 3) takes polynary alcohol and water to be mixed respectively,
Later, PVP is added into gained alcohol water mixed solvent, and carries out ultrasonic disperse and handles 30 ~ 60min, be made PVP a concentration of 20 ~
50g ∙l-1Homogeneous phase solution, it is spare；
Step 2: the preparation of high dispersive iron oxide microballoon
PVP homogeneous phase solutions made from a certain amount of step 1 are taken, and NaOH is added thereto, after being sufficiently stirred dissolving, NaOH is made
A concentration of 8 ~ 20 g l-1Mixed solution soluble ferric iron salt is added thereto later, make Fe in mixed solution3+It is a concentration of
0.1~0.6 mol ∙l-1, then, under constant agitation, gained mixed system is warming up to 40 ~ 80 DEG C, reaction 30 ~
60min obtains brown yellow solution, later, by gained brown yellow solution with 80% charging than transposition in autoclave, in 180
5 ~ 8h is reacted under ~ 220 DEG C of temperature condition is cooled to room temperature, and gained reaction product is centrifuged after reaction,
Remove a layer solid, later, using absolute ethyl alcohol and water it is carried out alternately wash 3 ~ 5 times, then, under the conditions of 40 ~ 60 DEG C into
Row 3 ~ 5h of vacuum drying, obtains high dispersive iron oxide microballoon, and vacuum is protected dry spare；
Step 3: the preparation of titania precursor body
PVP homogeneous phase solutions made from a certain amount of step 1 are taken, according to 5 ~ 9mol l-1Concentration proportioning, organic acid is added thereto,
And carry out ultrasonic disperse and handle 20 ~ 40min, and then according to 0.5 ~ 1mol l-1Concentration proportioning, titanate esters are added thereto,
Continue to be ultrasonically treated, until yellow transparent colloidal sol is obtained, it is spare；
Step 4: the coating of iron oxide microballoon
Addition according to iron oxide microballoon is 5 ~ 12 g l-1Proportioning, take iron oxide microballoon made from step 2 to be added to step
In yellow transparent colloidal sol made from rapid three, under constant agitation, 50 ~ 70 DEG C of progress slow evaporations are warming up to, until solvent
It is evaporated, later, 2 ~ 4h is handled at a temperature of gained gel is placed in 600 ~ 800 DEG C, titanium-oxide-coated iron oxide is obtained and is formed
Magnetic core micro mist, it is spare；
Step 5: the nitridation of titanium oxide coating
Titanium-oxide-coated magnetic core micro mist made from step 4 is placed in tube-type atmosphere furnace, to tube-type atmosphere furnace vacuumize process
Afterwards, it is controlled with 5 ~ 10 DEG C of min-1Heating rate be warming up to 400 ~ 500 DEG C, and carry out 1 ~ 2 h of heat preservation at such a temperature, so
Afterwards, with 150 ~ 180 mlmin-1Flow velocity NH is passed through into stove3, and tube-type atmosphere furnace is controlled with 5 ~ 10 DEG C of min-1Heating
Rate is continuously heating to 650 ~ 750 DEG C, and carries out 2 ~ 4h of heat preservation at such a temperature, later, by NH3It is 80 ~ 120 to be converted to flow velocity
ml·min-1Nitrogen, stop heating, coat the titanium nitride of core structure after cooled to room temperature to get the finished product of black gray expandable
Microspherical catalyst.
2. a kind of preparation method with the titanium nitride microspherical catalyst for coating core structure as described in claim 1, special
Sign is：In step 1, the polyalcohol is any one in ethylene glycol, diethylene glycol (DEG) and α-propylene glycol.
3. a kind of preparation method with the titanium nitride microspherical catalyst for coating core structure as described in claim 1, special
Sign is：In step 1, the model K30 of PVP used, molecular weight Mw=1 × 104。
4. a kind of preparation method with the titanium nitride microspherical catalyst for coating core structure as described in claim 1, special
Sign is：In step 2, the soluble ferric iron salt is ferric acetyl acetonade or 1- butyl -3- methylimidazole titanium tetrachlorides.
5. a kind of preparation method with the titanium nitride microspherical catalyst for coating core structure as described in claim 1, special
Sign is：In step 3, the organic acid is any one in acetic acid, citric acid and lactic acid.
6. a kind of preparation method with the titanium nitride microspherical catalyst for coating core structure as described in claim 1, special
Sign is：In step 3, the titanate esters are any one in butyl titanate, tetraisopropyl titanate and tetraethyl titanate
Kind.
7. a kind of preparation method with the titanium nitride microspherical catalyst for coating core structure as described in claim 1, special
Sign is：In step 1 and step 3, it is 240w that the ultrasonic disperse, which is handled using power, frequency is the super of 40kHz
Sonic generator.
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312218A (en) * | 2001-03-23 | 2001-09-12 | 中国科学院上海硅酸盐研究所 | Titania nitriding process for preparing nanometer titanium nitride powder |
| CN1416956A (en) * | 2001-11-01 | 2003-05-14 | 中国科学院广州能源研究所 | Megnetic nano composite photocatalyst and its prepn and use |
| CN101076400A (en) * | 2004-12-09 | 2007-11-21 | 瓦克化学有限公司 | Platinum catalysts that are supported on nanoscale titanium dioxide, use thereof in hydrosilylation, hydrosilylation method using said catalysts and compositions comprising said catalysts |
| CN101298321A (en) * | 2008-05-30 | 2008-11-05 | 河南大学 | Preparation of titanium nitride nanopower |
| CN101579623A (en) * | 2009-04-02 | 2009-11-18 | 天津海驰化工科技有限公司 | Preparation method of load type metal compound catalyst used for water treatment |
| WO2011096230A1 (en) * | 2010-02-08 | 2011-08-11 | 学校法人慈恵大学 | Magnetic particles, process for producing same, and medicinal preparation including magnetic particles |
| CN102302933A (en) * | 2011-06-23 | 2012-01-04 | 常州大学 | Method for preparing magnetic oxide hollow microsphere/titanium dioxide composite photocatalyst |
| CN104261487A (en) * | 2014-09-23 | 2015-01-07 | 南昌航空大学 | Method for preparing ferroferric oxide/graphene magnetic nano composite material by solvothermal one-step method |
| WO2015044964A1 (en) * | 2013-09-30 | 2015-04-02 | Council Of Scientific & Industrial Research | Magnetic nanoparticles decorated activated carbon nanocomposites for purification of water |
| CN104785264A (en) * | 2015-03-31 | 2015-07-22 | 上海大学 | Preparation method for Fe2O3/TiO2 porous ceramic with photocatalytic function |
| CN106517353A (en) * | 2016-11-02 | 2017-03-22 | 绥化学院 | Preparation method of alpha-Fe2O3/TiO2 nano-composite gas sensing material |
| CN106746711A (en) * | 2016-11-17 | 2017-05-31 | 陕西盛迈石油有限公司 | The method that ammonia reduction nitridation method prepares TiAlN thin film |
| CN107469828A (en) * | 2017-07-05 | 2017-12-15 | 杭州师范大学 | A kind of core shell structure support type tungsten composite catalyst and its preparation method and application |
-
2018
- 2018-02-02 CN CN201810104308.9A patent/CN108325553B/en not_active Expired - Fee Related
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312218A (en) * | 2001-03-23 | 2001-09-12 | 中国科学院上海硅酸盐研究所 | Titania nitriding process for preparing nanometer titanium nitride powder |
| CN1416956A (en) * | 2001-11-01 | 2003-05-14 | 中国科学院广州能源研究所 | Megnetic nano composite photocatalyst and its prepn and use |
| CN101076400A (en) * | 2004-12-09 | 2007-11-21 | 瓦克化学有限公司 | Platinum catalysts that are supported on nanoscale titanium dioxide, use thereof in hydrosilylation, hydrosilylation method using said catalysts and compositions comprising said catalysts |
| CN101298321A (en) * | 2008-05-30 | 2008-11-05 | 河南大学 | Preparation of titanium nitride nanopower |
| CN101579623A (en) * | 2009-04-02 | 2009-11-18 | 天津海驰化工科技有限公司 | Preparation method of load type metal compound catalyst used for water treatment |
| WO2011096230A1 (en) * | 2010-02-08 | 2011-08-11 | 学校法人慈恵大学 | Magnetic particles, process for producing same, and medicinal preparation including magnetic particles |
| CN102302933A (en) * | 2011-06-23 | 2012-01-04 | 常州大学 | Method for preparing magnetic oxide hollow microsphere/titanium dioxide composite photocatalyst |
| WO2015044964A1 (en) * | 2013-09-30 | 2015-04-02 | Council Of Scientific & Industrial Research | Magnetic nanoparticles decorated activated carbon nanocomposites for purification of water |
| CN104261487A (en) * | 2014-09-23 | 2015-01-07 | 南昌航空大学 | Method for preparing ferroferric oxide/graphene magnetic nano composite material by solvothermal one-step method |
| CN104785264A (en) * | 2015-03-31 | 2015-07-22 | 上海大学 | Preparation method for Fe2O3/TiO2 porous ceramic with photocatalytic function |
| CN106517353A (en) * | 2016-11-02 | 2017-03-22 | 绥化学院 | Preparation method of alpha-Fe2O3/TiO2 nano-composite gas sensing material |
| CN106746711A (en) * | 2016-11-17 | 2017-05-31 | 陕西盛迈石油有限公司 | The method that ammonia reduction nitridation method prepares TiAlN thin film |
| CN107469828A (en) * | 2017-07-05 | 2017-12-15 | 杭州师范大学 | A kind of core shell structure support type tungsten composite catalyst and its preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| LUSSIER A ET AL.: "Characterization for strontium titinate/Fe3O4 and TiN/Fe3O4 interfaces", 《JOURNAL OF VACUUM SCIENCE & TECHNOLOGY B》 * |
| O.V. KOMOVA ET AL.: "Improved low-temperature hydrogen generation from NH3BH3 and TiO2 composites pretreated with water", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 * |
| 王月影等: "氨硼烷水解释氢研究进展", 《西部皮革》 * |
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