CN114162856A - Method for synthesizing iron-doped titanium oxide at high temperature and high pressure - Google Patents
Method for synthesizing iron-doped titanium oxide at high temperature and high pressure Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 73
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 19
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 69
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 24
- 239000001301 oxygen Substances 0.000 claims abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052742 iron Inorganic materials 0.000 claims abstract description 23
- 239000010936 titanium Substances 0.000 claims abstract description 20
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007858 starting material Substances 0.000 claims abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 50
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 31
- 229910052697 platinum Inorganic materials 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 20
- 238000000227 grinding Methods 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- 238000003786 synthesis reaction Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- 235000012431 wafers Nutrition 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 9
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 230000005540 biological transmission Effects 0.000 claims description 6
- 229910003460 diamond Inorganic materials 0.000 claims description 6
- 239000010432 diamond Substances 0.000 claims description 6
- 244000137852 Petrea volubilis Species 0.000 claims description 5
- 238000005498 polishing Methods 0.000 claims description 5
- 238000010791 quenching Methods 0.000 claims description 5
- 230000000171 quenching effect Effects 0.000 claims description 5
- 229910003079 TiO5 Inorganic materials 0.000 claims description 4
- JCDAAXRCMMPNBO-UHFFFAOYSA-N iron(3+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Ti+4].[Fe+3].[Fe+3] JCDAAXRCMMPNBO-UHFFFAOYSA-N 0.000 claims description 3
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 abstract description 6
- 230000001699 photocatalysis Effects 0.000 abstract description 5
- 238000005070 sampling Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 229910052903 pyrophyllite Inorganic materials 0.000 description 6
- 239000012071 phase Substances 0.000 description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910001447 ferric ion Inorganic materials 0.000 description 3
- 150000002500 ions Chemical group 0.000 description 3
- -1 iron ions Chemical class 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000000137 annealing Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- IXQWNVPHFNLUGD-UHFFFAOYSA-N iron titanium Chemical compound [Ti].[Fe] IXQWNVPHFNLUGD-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- YLMGFJXSLBMXHK-UHFFFAOYSA-M potassium perchlorate Chemical compound [K+].[O-]Cl(=O)(=O)=O YLMGFJXSLBMXHK-UHFFFAOYSA-M 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/08—Drying; Calcining ; After treatment of titanium oxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
- C01P2002/54—Solid solutions containing elements as dopants one element only
Abstract
The invention discloses a method for synthesizing iron-doped titanium oxide at high temperature and high pressure, which uses analytically pure titanium dioxide TiO2And analytically pure iron oxide Fe2O3In a molar ratio of [2(1-x)]X is uniformly mixed and ground as a starting material, wherein x is the doping amount of iron, 0<x is less than or equal to 0.15, and iron-doped titanium oxide (Ti) is obtained through high-temperature high-pressure reaction1‑xFex)O2‑δAnd (3) sampling. The high-temperature high-pressure reaction is carried out in a closed environment with ultrahigh oxygen pressure, the controllable iron doping area is greatly improved, the limit concentration reported to be 5% at present is extended to 15%, and an experimental basis is laid for further researching the quantitative relation between the photocatalytic efficiency and the iron doping concentration.
Description
Technical Field
The invention relates to the field of research of materials science, and relates to a method for synthesizing iron-doped titanium oxide at high temperature and high pressure.
Background
The prevention and treatment measures of water pollution are one of the core problems of the current environmental protection, and titanium oxide TiO2The process of photocatalytic degradation of organic matters has extremely superior effect on treating water pollution. Because the titanium oxide is in an ultraviolet region due to high excitation energy of a forbidden band of the titanium oxide, the titanium oxide can only sense ultraviolet light accounting for about 5% of sunlight and is insensitive to visible light, so that the photocatalytic efficiency of the titanium oxide is seriously influenced. Research shows that iron ions Fe are doped in titanium oxide3+A new energy band can be formed between the conduction band bottom and the valence band top, response can be generated to photons with lower energy, and the photoresponse wavelength is enabled to move towards the visible light direction, so that the utilization efficiency of photocatalysis is greatly improved. The existing method for synthesizing iron-doped titanium oxide is mainly a hydrothermal method, and has two obvious technical defects: (1) the highest doped amount of iron is 5 percent, so that the controllable doped region which can quantitatively research the photocatalytic efficiency of the iron-doped titanium oxide is too narrow at present, and the iron ions Fe in the titanium oxide crystal lattice3+The maximum doping concentration of (a) is not clear; (2) the sample obtained by the hydrothermal method is generally a nanocrystal, the crystallinity is poor, the crystal structure and the component uniformity are unknown, and meanwhile, the influence of structural water and adsorbed water can interfere with the quantitative research of the catalytic property along with the change of the iron content. Therefore, reasonably improving the synthesis technology and experimentally obtaining the titanium dioxide with good crystallinity, uniform components and higher doped iron concentration is a technical problem to be solved at present.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a high-temperature high-pressure synthesis method of titanium oxide (Ti) with good crystallinity, uniform components and higher doped iron concentration1-xFex)O2-δSo as to solve the technical problem existing at present.
The technical scheme of the invention is as follows: high-temperature high-pressure synthesis of iron-doped titanium oxide (Ti)1-xFex)O2-δThe method comprises the following steps:
step 1, use of analytically pure titanium oxide TiO2And analytically pure iron oxide Fe2O3In a molar ratio of [2(1-x)]X as the starting material by mixing and grindingWherein x is the doping amount of iron, 0<x≤0.15；
Step 2, using a powder tablet machine to place the mixture powder in a phi 6 grinding tool to be pressed into a phi 6 multiplied by 5mm cylinder shape; analytically pure potassium perchlorate KClO4Placing the powder in a phi 6 grinding tool to press into a phi 6 x 2mm wafer, and adding KClO4Disc-mixture cylinder-KClO4The wafers are sequentially stacked and put into a platinum snap fastener with the inner diameter of phi 6mm and the thickness of 0.1mm for sealing, and KClO4Providing an oxygen source; placing the sealed platinum cylinder in an h-BN tube, and taking the h-BN as a pressure transmission medium;
step 3, assembling the h-BN pipe provided with the sample in the step 2 in a high-pressure synthesis assembly block and placing the h-BN pipe in a cubic apparatus large press for high-temperature high-pressure reaction;
step 4, after the high-temperature high-pressure reaction is finished, taking out the platinum-coated cylindrical sample, cutting the platinum tube by using a diamond cutter, taking out the sample, and polishing the upper and lower KCl layers of the sample by using fine sand paper to obtain the iron-doped titanium oxide (Ti)1- xFex)O2-δ。
Step 2, the h-BN pipe is operated as follows: drilling a phi 6mm hole in the center of a phi 10mm h-BN rod on a lathe to form an h-BN tube, inserting a sample into the tube, and sealing two ends of the h-BN tube by taking a phi 6mm h-BN sheet with the thickness of 2 mm.
The method for assembling the h-BN pipe in the high-pressure synthesis assembly block in the step 3 comprises the following specific operations: selecting a pyrophyllite block, and punching a phi 12mm circular through hole in the center of the pyrophyllite block; a circular graphite heating furnace with the outer diameter of 12mm and the inner diameter of phi 10mm is sleeved in the circular through hole; placing a 10mm h-BN tube sealed sample in the middle of a graphite heating furnace; the upper end and the lower end of the round graphite heating furnace are sealed by pyrophyllite plugs.
And 3, under the high-temperature and high-pressure reaction condition, increasing the pressure to 1-3GPa, then heating to 700-800 ℃, maintaining the pressure and preserving the heat for 1h, and then quenching.
The synthetic product obtained in the step 4 is 0<x is less than or equal to 0.15, and the product is iron-doped titanium oxide (Ti)1-xFex)O2-δSingle phase, no other impurities; when x is>0.15, the product is iron-doped titanium oxide and iron titanate Fe3TiO5Mixed phase of Fe3+Cannot continue into the titanium oxide lattice by doping.
Step 4, the obtained high-temperature high-pressure synthesized iron-doped titanium oxide (Ti)1-xFex)O2-δThe method of (1), wherein the obtained sample is gray powder, and becomes darker with the increase of the content of doped iron.
The synthetic product obtained in the step 4 is iron-doped titanium oxide (Ti)1-xFex)O2-δ，0<x is less than or equal to 0.15, no other impurities exist, the crystal structure is a tetragonal system P42/mnm, and the lattice parameter
The invention has the advantages that:
experimental studies show that the difficulty in synthesizing iron-doped titanium oxide is to increase the iron doping concentration and ensure the uniformity of the titanium iron component. Iron-doped titanium oxide (Ti) according to the semiconductor doping principle1-xFex)O2-δDoping the semiconductor for the hole type, i.e. doping of iron, causes the creation of oxygen vacancies δ in the titanium oxide lattice:
(1-x)TiO2+(x/2)Fe2O3+ (x/2-delta) O (provided by the reaction environment) → (Ti)1-xFex)O2-δ
In fact, the generation of oxygen vacancy δ may destroy the stability of the crystal lattice, so there is an upper limit to the iron doping concentration x and it is strictly limited by the synthesis conditions and the reaction environment. Because of Fe3+And Ti4+The radius is close to the size requirement of ion substitution, so the iron doping concentration is mainly influenced by the oxygen pressure of the reaction environment, namely the larger the oxygen pressure is, the larger the doping amount x is, and the smaller the oxygen vacancy delta in the product is. This explains that the synthesis of iron-doped titanium oxide at atmospheric pressure is limited by the low ambient oxygen pressure, so that the doping concentration is very low and cannot exceed 5%. Compared with the prior art, the doping concentration can be further improved by a high oxygen pressure and strong oxidation environment. Based on the method, the iron-doped titanium oxide is synthesized by high-oxygen pressure and strong oxidation assembly under extreme conditions of high temperature and high pressure, and the uniform doping and the concentration limit reaching 1 are explored5% so as to cover all the regions under-doped-optimally doped-over-doped, described in detail as:
(1) the potassium perchlorate provides an oxygen source and can be decomposed at about 400 ℃ to fully release oxygen. Compared with conventional peroxide oxygen sources, e.g. SrO2、BaO2Equal, O released per unit mass of potassium perchlorate2At most, has the advantage of good chemical stability. The platinum snap fastener can seal oxygen in the sample cavity under the high pressure condition, the oxygen pressure in the sample cavity is equal to the pressure in the press cavity, and ultrahigh oxygen pressure of tens of thousands of atmospheric pressure grades of GPa is formed in the sample cavity. Fe2O3Under the annealing action of ultrahigh oxygen pressure, using FeO2-δForm doping into TiO2A crystal lattice. The ultrahigh oxygen pressure can effectively reduce oxygen vacancy, so that the true valence of iron participating in the reaction is greater than +3, and the iron is as close to Ti as possible4+The tetravalent matching valence of (a) finally forces the doping amount x of iron to reach the limit concentration of 0.15. In addition, the doping of iron can obviously improve the density of titanium oxide, and high pressure is more prone to the generation of high-density products, so that the high-pressure environment is more favorable for synthesizing titanium oxide doped with high iron concentration than normal pressure. When the nominal mixture ratio x>0.15, Fe can not enter titanium oxide crystal lattice continuously, Fe appears2TiO5A hetero-phase, which marks the limit concentration of 15% of doping of ferric ions that can be tolerated by the titanium oxide lattice, which is also the maximum doping amount of iron reported so far;
(2) compared with the normal pressure condition, the high temperature and high pressure condition can greatly accelerate the diffusion rate of solid phase particles, lead the ferrotitanium to be in a dispersion system with increased entropy, avoid the generation of iron clusters and improve the uniformity of a sample to the maximum extent. Meanwhile, the solid-phase reaction is carried out under the anhydrous condition, so that the interference of hydroxyl on a doping mechanism is avoided. In addition, the crystallinity of the sample can be greatly improved under the conditions of high temperature and high pressure, the quality of spectroscopic data is ensured, the grain boundary effect can be further eliminated by longer reaction time, and the possibility is provided for the growth of crystals and the research of crystal structures;
(3) the pressure of 1-3GPa is the safe pressure of a domestic cubic press, the temperature of 700-800 ℃ is the optimal temperature for synthesizing iron-doped titanium oxide, the temperature is lower than 700 ℃, the solid-phase reaction is slow, and the reaction can not be completely carried out within 1 hour; the temperature is higher than 800 ℃, the decomposition product KCl of the potassium perchlorate is melted and flows in the sample cavity, and the difficulty of separating iron-doped titanium oxide and KCl is increased;
(4) the method for synthesizing iron-doped titanium oxide by high-temperature, high-pressure and high-oxygen-pressure annealing is also suitable for doping other trivalent ions, such as Al3+，Cr3+Etc., can be further expanded to a variety of trivalent ion-doped titanium oxides, which are expected to achieve optimal doping for their photocatalytic efficiency by varying the doping ion species and concentration.
Detailed Description
Example 1:
high-temperature high-pressure synthesis of iron-doped titanium oxide (Ti)0.95Fe0.05)O2-δThe method comprises the following steps:
step 1, using analytically pure titanium dioxide TiO2And analytically pure iron oxide Fe2O3Uniformly mixing and grinding the raw materials as initial raw materials in a molar ratio of 38: 1;
step 2, using a powder tablet machine to place the mixture powder in a phi 6 grinding tool to be pressed into a phi 6 multiplied by 5mm cylinder shape; analytically pure potassium perchlorate KClO4Placing the powder in a phi 6 grinding tool to press into a phi 6 x 2mm wafer, and adding KClO4Disc-mixture cylinder-KClO4The wafers are sequentially stacked and put into a platinum snap fastener with the inner diameter of phi 6mm and the thickness of 0.1mm for sealing, and KClO4Providing an oxygen source; placing the sealed platinum cylinder in an h-BN tube, and taking the h-BN as a pressure transmission medium;
step 3, assembling the h-BN pipe provided with the sample in the step 2 in a high-pressure synthesis assembly block and placing the h-BN pipe in a cubic apparatus large press for high-temperature high-pressure reaction, wherein the high-temperature high-pressure reaction condition is that the pressure is increased to 1GPa, then the temperature is increased to 700 ℃, and the pressure and the heat are maintained for 1h and then the h-BN pipe is quenched;
step 4, after the high-temperature high-pressure reaction is finished, taking out the platinum-coated cylindrical sample, cutting the platinum tube by using a diamond cutter, taking out the sample, and polishing the upper and lower KCl layers of the sample by using fine sand paper to obtain the iron-doped titanium oxide (Ti)0.95Fe0.05)O2-δAnd no other impurities.
Example 2:
high-temperature high-pressure synthesis of iron-doped titanium oxide (Ti)0.9Fe0.1)O2-δThe method comprises the following steps:
step 1, using analytically pure titanium dioxide TiO2And analytically pure iron oxide Fe2O3Uniformly mixing and grinding the raw materials as initial raw materials in a molar ratio of 18: 1;
step 2, using a powder tablet machine to place the mixture powder in a phi 6 grinding tool to be pressed into a phi 6 multiplied by 5mm cylinder shape; analytically pure potassium perchlorate KClO4Placing the powder in a phi 6 grinding tool to press into a phi 6 x 2mm wafer, and adding KClO4Disc-mixture cylinder-KClO4The wafers are sequentially stacked and put into a platinum snap fastener with the inner diameter of phi 6mm and the thickness of 0.1mm for sealing, and KClO4Providing an oxygen source; placing the sealed platinum cylinder in an h-BN tube, and taking the h-BN as a pressure transmission medium;
step 3, assembling the h-BN pipe provided with the sample in the step 2 in a high-pressure synthesis assembly block and placing the h-BN pipe in a cubic apparatus large press for high-temperature high-pressure reaction, wherein the high-temperature high-pressure reaction condition is that the pressure is increased to 2GPa, then the temperature is increased to 750 ℃, and the pressure and heat preservation are carried out for 1h, and then quenching is carried out;
step 4, after the high-temperature high-pressure reaction is finished, taking out the platinum-coated cylindrical sample, cutting the platinum tube by using a diamond cutter, taking out the sample, and polishing the upper and lower KCl layers of the sample by using fine sand paper to obtain the iron-doped titanium oxide (Ti)0.9Fe0.1)O2-δAnd no other impurities.
Example 3:
high-temperature high-pressure synthesis of iron-doped titanium oxide (Ti)0.85Fe0.15)O2-δThe method comprises the following steps:
step 1, using analytically pure titanium dioxide TiO2And analytically pure iron oxide Fe2O3Uniformly mixing and grinding the raw materials as initial raw materials in a molar ratio of 34: 3;
step 2, using a powder tablet machine to place the mixture powder in a phi 6 grinding tool to be pressed into a phi 6 multiplied by 5mm cylinder shape; analytically pure potassium perchlorate KClO4Placing the powder in a phi 6 grinding tool to press into a phi 6 x 2mm wafer, and adding KClO4Disc-mixture cylinder-KClO4The wafers are sequentially stacked and put into a platinum snap fastener with the inner diameter of phi 6mm and the thickness of 0.1mm for sealing, and KClO4Providing an oxygen source; placing the sealed platinum cylinder in an h-BN tube, and taking the h-BN as a pressure transmission medium;
step 3, assembling the h-BN pipe provided with the sample in the step 2 in a high-pressure synthesis assembly block and placing the h-BN pipe in a cubic apparatus large press for high-temperature high-pressure reaction, wherein the high-temperature high-pressure reaction condition is that the pressure is increased to 3GPa, then the temperature is increased to 800 ℃, and the pressure and heat preservation is carried out for 1h, and then quenching is carried out;
step 4, after the high-temperature high-pressure reaction is finished, taking out the platinum-coated cylindrical sample, cutting the platinum tube by using a diamond cutter, taking out the sample, and polishing the upper and lower KCl layers of the sample by using fine sand paper to obtain the iron-doped titanium oxide (Ti)0.85Fe0.15)O2-δ. No other impurities.
Comparative example:
step 1, using analytically pure titanium dioxide TiO2And analytically pure iron oxide Fe2O3Uniformly mixing and grinding the raw materials as initial raw materials in a molar ratio of 8: 1;
step 2, using a powder tablet machine to place the mixture powder in a phi 6 grinding tool to be pressed into a phi 6 multiplied by 5mm cylinder shape; analytically pure potassium perchlorate KClO4Placing the powder in a phi 6 grinding tool to press into a phi 6 x 2mm wafer, and adding KClO4Disc-mixture cylinder-KClO4The wafers are sequentially stacked and put into a platinum snap fastener with the inner diameter of phi 6mm and the thickness of 0.1mm for sealing, and KClO4Providing an oxygen source; placing the sealed platinum cylinder in an h-BN tube, and taking the h-BN as a pressure transmission medium;
step 3, assembling the h-BN pipe provided with the sample in the step 2 in a high-pressure synthesis assembly block and placing the h-BN pipe in a cubic apparatus large press for high-temperature high-pressure reaction, wherein the high-temperature high-pressure reaction condition is that the pressure is increased to 2GPa, then the temperature is increased to 750 ℃, and the pressure and heat preservation are carried out for 1h, and then quenching is carried out;
step 4, taking out the cylindrical sample wrapped by the platinum after the high-temperature high-pressure reaction is finished, cutting the platinum tube by using a diamond cutter, taking out the sample, and using a thin tubeSanding the KCl layers on and under the sample to obtain the product of iron-doped titanium oxide and iron titanate Fe3TiO5Mixing the phases.
In addition, the h-BN tubes described in examples 1-3 and the comparative examples were operated as follows: drilling a phi 6mm hole in the center of an h-BN rod with the size of phi 10mm on a lathe to form an h-BN pipe, inserting a sample into the pipe, sealing two ends of the h-BN pipe by h 6mm and 2mm in thickness, and assembling the h-BN pipe in a high-pressure synthesis assembly block, wherein the specific operation comprises the following steps: selecting a pyrophyllite block, and punching a phi 12mm circular through hole in the center of the pyrophyllite block; a circular graphite heating furnace with the outer diameter of 12mm and the inner diameter of phi 10mm is sleeved in the circular through hole; placing a 10mm h-BN tube sealed sample in the middle of a graphite heating furnace; the upper end and the lower end of the round graphite heating furnace are sealed by pyrophyllite plugs.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (5)
1. A method for synthesizing iron-doped titanium oxide at high temperature and high pressure is characterized by comprising the following steps:
step 1, use of analytically pure titanium oxide TiO2And analytically pure iron oxide Fe2O3In a molar ratio of [2(1-x)]X is uniformly mixed and ground as a starting material, wherein x is the doping amount of iron, 0<x≤0.15；
Step 2, using a powder tablet machine to place the mixture powder in a phi 6 grinding tool to be pressed into a phi 6 multiplied by 5mm cylinder shape; analytically pure potassium perchlorate KClO4Placing the powder in a phi 6 grinding tool to press into a phi 6 x 2mm wafer, and adding KClO4Disc-mixture cylinder-KClO4Sequentially stacking the wafers, sealing in a platinum snap fastener with an inner diameter of phi 6mm and a thickness of 0.1mm, and sealingThe sealed platinum cylinder is arranged in an h-BN pipe, and the h-BN is used as a pressure transmission medium;
step 3, assembling the h-BN pipe provided with the sample in the step 2 in a high-pressure synthesis assembly block and placing the h-BN pipe in a cubic apparatus large press for high-temperature high-pressure reaction;
step 4, after the high-temperature high-pressure reaction is finished, taking out the platinum-coated cylindrical sample, cutting the platinum tube by using a diamond cutter, taking out the sample, and polishing the upper and lower KCl layers of the sample by using fine sand paper to obtain the iron-doped titanium oxide (Ti)1-xFex)O2-δAnd delta is an oxygen vacancy.
2. The method according to claim 1, wherein the high temperature and high pressure reaction conditions in step 3 are that the pressure is increased to 1-3GPa, then the temperature is increased to 800 ℃ at 700 ℃ and the temperature is maintained for 1h, and then the quenching is carried out.
3. The method of claim 1, wherein 0 is used as<x is less than or equal to 0.15, and the iron-doped titanium oxide (Ti) obtained in the step 41-xFex)O2-δIs a single phase without other impurities; when x is>0.15, the product obtained in step 4 is iron-doped titanium oxide and iron titanate Fe3TiO5Mixing the phases.
4. The iron-doped titanium oxide obtained by the method according to claim 1, wherein the iron-doped titanium oxide sample is a gray powder which becomes darker as the doped iron content increases.
5. The iron-doped titanium oxide obtained by the method according to claim 1, wherein the iron-doped titanium oxide sample has the chemical formula (Ti)1-xFex)O2-δ，0<x is less than or equal to 0.15, no other impurities exist, the crystal structure is a tetragonal system, the space group is P42/mnm, and the lattice parameter
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