CN114162856B - Method for doping titanium oxide by using Cheng Tie under high temperature and high pressure - Google Patents
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 51
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 89
- 229910052742 iron Inorganic materials 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 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 12
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 50
- 229910052697 platinum Inorganic materials 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 21
- 238000000227 grinding Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 14
- 235000012431 wafers Nutrition 0.000 claims description 12
- 238000007789 sealing Methods 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 8
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims description 8
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 8
- 244000137852 Petrea volubilis Species 0.000 claims description 6
- 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
- 239000012535 impurity Substances 0.000 claims description 6
- 238000010791 quenching Methods 0.000 claims description 6
- 230000000171 quenching effect Effects 0.000 claims description 6
- 206010021143 Hypoxia Diseases 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 4
- 229910003087 TiOx Inorganic materials 0.000 claims description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [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
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 21
- 239000001301 oxygen Substances 0.000 abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 20
- 230000001699 photocatalysis Effects 0.000 abstract description 5
- 239000004408 titanium dioxide Substances 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052903 pyrophyllite Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 150000002500 ions Chemical group 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- -1 iron ion Chemical class 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 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
- 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 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 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
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910004116 SrO 2 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 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
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 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
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction 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 doping titanium oxide by Cheng Tie under high temperature and high pressure, which uses analytically pure titanium dioxide TiO 2 And analytically pure iron oxide Fe 2 O 3 In a molar ratio [2 (1-x)]X is the doping amount of iron, 0<x is less than or equal to 0.15, and the iron doped titanium oxide (Ti) is obtained through high temperature and high pressure reaction 1‑x Fe x )O 2‑δ And (3) a sample. The high-temperature high-pressure reaction is carried out in a closed environment with ultrahigh oxygen pressure, so that the doping area of controllable iron is greatly improved, the limit concentration reported to 5% at present is extended to 15%, and an experimental foundation 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 material science research, and relates to a method for doping titanium oxide by Cheng Tie under high temperature and high pressure.
Background
The measure for preventing and controlling water pollution is one of the core problems of the current environmental protection, and titanium oxide TiO 2 The process of photocatalytic degradation of organic matters has extremely excellent effect on water pollution treatment. Because titanium oxide has high self forbidden band excitation energy and is in an ultraviolet region, only ultraviolet light accounting for about 5% of sunlight can be sensed, but the titanium oxide is insensitive to visible light, and the photocatalytic efficiency of the titanium oxide is seriously affected. Research shows that iron ion Fe is doped in titanium oxide 3+ The novel energy band can be formed between the conduction band bottom and the valence band top, and the novel energy band can respond to photons with lower energy, so that the light response wavelength moves towards the visible light direction, and the utilization efficiency of photocatalysis is greatly improved. The current method for synthesizing iron-doped titanium oxide is mainly a hydrothermal method, and has two obvious technical defects: (1) The highest doping amount of iron is 5%, which makes the controllable doping area for quantitatively researching the photocatalytic efficiency of the iron doped titanium oxide be too narrow, and the iron ion Fe in the titanium oxide crystal lattice 3+ The maximum doping concentration of (2) is not yet clear; (2) The sample obtained by the hydrothermal method is generally nanocrystalline, has poor crystallinity, has unknown crystal structure and component uniformity, and can be influenced by structural water and adsorbed water to interfere quantitative research of the catalytic property changing along with the iron content. Therefore, reasonably improving the synthesis technology, experimentally obtaining titanium dioxide with good crystallinity, uniform composition and higher doped iron concentration is a technical problem to be solved at present.
Disclosure of Invention
The invention aims to solve the technical problems that: provides a titanium oxide (Ti) with good high-temperature high-pressure compression crystallinity, uniform composition and higher doped iron concentration 1-x Fe x )O 2-δ To solve the technical problems existing at present.
The technical scheme of the invention is as follows: high temperature high pressure Cheng Tie doped titanium oxide (Ti) 1-x Fe x )O 2-δ Comprising the following steps:
step 1, use of analytically pure TiOx TiO 2 And analytically pure iron oxideFe 2 O 3 In a molar ratio [2 (1-x)]X is the doping amount of iron, 0<x≤0.15；
Step 2, placing the mixture powder into a phi 6 grinding tool by using a powder tablet press to be pressed into a phi 6 multiplied by 5mm cylinder; analytically pure potassium perchlorate KClO 4 Placing the powder into a phi 6 grinding tool to form a phi 6 multiplied by 2mm wafer, and adding KClO 4 Wafer-mixture cylinder-KClO 4 The wafers are sequentially stacked and put into a platinum snap fastener with the inner diameter phi of 6mm and the thickness of 0.1mm for sealing, KClO 4 Providing 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, the h-BN tube with the sample in the step 2 is assembled in a high-pressure assembling block and placed in a hexahedral top large press for high-temperature high-pressure reaction;
step 4, after the high-temperature high-pressure reaction is finished, taking out a cylindrical sample wrapped by platinum, cutting a platinum tube by using a diamond cutter, taking out the sample, and polishing KCl layers on the upper and lower sides of the sample by using fine sand paper to obtain iron-doped titanium oxide (Ti 1- x Fe x )O 2-δ 。
The h-BN tube in the step 2 is specifically operated as follows: and (3) drilling a Kong Zuocheng h-BN pipe with the diameter of 6mm at the center of an h-BN rod with the diameter of 10mm on a lathe, and plugging a sample into the pipe, wherein h-BN sheets with the thickness of 2mm and the diameter of 6mm are taken at two ends to seal.
The method for assembling the h-BN tube into the high pressure synthesis assembly block in the step 3 comprises the following specific operations: selecting a pyrophyllite block, and punching a circular through hole with the diameter of 12mm in the center of the pyrophyllite block; a circular graphite heating furnace with the outer diameter of 12mm and the inner diameter phi of 10mm is sleeved in the circular through hole; placing a sample sealed by an h-BN tube with the thickness of 10mm in the middle of a graphite heating furnace; and sealing the upper end and the lower end of the round graphite heating furnace by using pyrophyllite plugs.
And 3, the high-temperature high-pressure reaction condition is that the pressure is increased to 1-3GPa, then the temperature is increased to 700-800 ℃, and the quenching is performed after the pressure maintaining and heat preserving for 1 hour.
The synthetic product obtained in step 4, when 0<x is less than or equal to 0.15, and the product is iron doped titanium oxide (Ti) 1-x Fe x )O 2-δ Single phase, free of other impuritiesThe method comprises the steps of carrying out a first treatment on the surface of the When x is>0.15, the products are iron-doped titanium oxide and iron titanate Fe 3 TiO 5 Mixed phase, fe 3+ It is not possible to continue into the titanium oxide lattice by doping.
The high temperature and high pressure Cheng Tie doped titanium oxide (Ti) 1-x Fe x )O 2-δ The resulting sample was a gray powder, which darkened with increasing doped iron content.
The synthesized product obtained in the step 4 is iron doped titanium oxide (Ti 1-x Fe x )O 2-δ ，0<x is less than or equal to 0.15, no other impurities exist, the crystal structure is tetragonal system P42/mn, and the lattice parameter is
The invention has the innovation points and beneficial effects that:
experimental research shows that the synthesis of iron-doped titanium oxide has the difficulty of increasing the iron doping concentration and ensuring the uniformity of ferrotitanium components. According to the semiconductor doping principle, iron-doped titanium oxide (Ti 1-x Fe x )O 2-δ As a hole-doped semiconductor, i.e. the doping of iron causes oxygen vacancies δ to be created in the titanium oxide lattice:
(1-x)TiO 2 +(x/2)Fe 2 O 3 ++ (x/2-. Delta.) O (provided by the reaction environment) → (Ti) 1-x Fe x )O 2-δ
In fact, the creation of oxygen deficiency δ destroys the stability of the crystal lattice, so that the iron doping concentration x presents an upper limit and is strictly constrained by the synthesis conditions and the reaction environment. Because of Fe 3+ And Ti is 4+ The radius is close to meet the size requirement of ion substitution, so that the iron doping concentration is mainly influenced by the oxygen pressure of the reaction environment, namely, the larger the ambient oxygen pressure is, the larger the doping amount x is and the smaller the oxygen deficiency delta is in the product. According to the explanation, the iron-doped titanium oxide is synthesized under normal pressure, and the doping concentration is very low and cannot exceed 5% due to the limitation of lower ambient oxygen pressure. Compared with the prior art, the high oxygen pressure and strong oxidation environment can further improve the doping concentration. Based on the above, the invention designs the high oxygen pressure under the extreme conditions of high temperature and high pressure,The iron-doped titanium oxide is synthesized by strong oxidation assembly, and the doping uniformity and the concentration limit reaching 15% are explored so as to cover all the areas of under doping, optimal doping and over doping, and the method is specifically described as follows:
(1) The potassium perchlorate provides an oxygen source and can decompose and fully release oxygen at about 400 ℃. Compared with the conventional peroxide oxygen source, e.g. SrO 2 、BaO 2 Etc., per unit mass of potassium perchlorate-released O 2 Most, and has the advantage of good chemical stability. The platinum snap fastener can seal oxygen in the sample cavity under the high pressure condition, and the oxygen pressure in the sample cavity is equal to the pressure in the press cavity, namely, the ultra-high oxygen pressure with the level of tens of thousands of atmosphere GPa is formed in the sample cavity. Fe (Fe) 2 O 3 Under the annealing action of ultrahigh oxygen pressure, feO is adopted 2-δ Form doping into TiO 2 Lattice. The ultrahigh oxygen pressure can effectively reduce oxygen deficiency, and lead the true valence of iron to participate in the reaction to be more than +3, so that the iron is as close to Ti as possible 4+ The doping amount x of iron is finally forced 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 beneficial to the synthesis of the titanium oxide doped with high iron concentration compared with normal pressure. When the nominal proportion is x>0.15, fe can not enter the titanium oxide crystal lattice continuously, and Fe appears 2 TiO 5 A hetero-phase, which marks the limit concentration of ferric ion doping that 15% is tolerated by the titanium oxide lattice, is also the maximum doping level of iron reported so far;
(2) Compared with normal pressure, the high temperature and high pressure condition can greatly accelerate the diffusion rate of solid phase particles, can lead the ferrotitanium to be in a dispersion system with increased entropy in solid solution, avoid the generation of iron clusters and furthest improve the uniformity of samples. 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 high temperature and high pressure condition can greatly improve the crystallinity of the sample, ensure the quality of the spectroscopic data, and the longer reaction time can further eliminate the grain boundary effect, thereby providing possibility for the growth of crystals and the study of crystal structures;
(3) The pressure of 1-3GPa set by the method is the safe pressure of a domestic hexahedral press, the temperature of 700-800 ℃ is the optimal temperature for synthesizing the iron-doped titanium oxide, the temperature is lower than 700 ℃, the solid phase reaction is slower, and the reaction can not be completely carried out within 1 hour; the temperature is higher than 800 ℃, and the potassium perchlorate decomposition product KCl is melted and flows in the sample cavity, so that the difficulty of separating the iron-doped titanium oxide from the KCl is increased;
(4) The method for synthesizing the iron-doped titanium oxide by high-temperature, high-pressure and high-oxygen pressure annealing is also suitable for doping with other trivalent ions, such as Al 3+ ，Cr 3+ And the like, can be further expanded into various trivalent ion doped titanium oxides, and is expected to achieve optimal doping of the photocatalytic efficiency by changing the type and concentration of the doped ions.
Detailed Description
Example 1:
high temperature high pressure Cheng Tie doped titanium oxide (Ti) 0.95 Fe 0.05 )O 2-δ Comprising the following steps:
step 1, use of analytically pure TiOTiO 2 And analytically pure iron oxide Fe 2 O 3 Uniformly mixing and grinding the raw materials in a molar ratio of 38:1 to obtain a starting raw material;
step 2, placing the mixture powder into a phi 6 grinding tool by using a powder tablet press to be pressed into a phi 6 multiplied by 5mm cylinder; analytically pure potassium perchlorate KClO 4 Placing the powder into a phi 6 grinding tool to form a phi 6 multiplied by 2mm wafer, and adding KClO 4 Wafer-mixture cylinder-KClO 4 The wafers are sequentially stacked and put into a platinum snap fastener with the inner diameter phi of 6mm and the thickness of 0.1mm for sealing, KClO 4 Providing 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, the h-BN tube with the sample in the step 2 is assembled in a high-pressure assembling block and placed in a hexahedral large press for high-temperature and high-pressure reaction, wherein the high-temperature and high-pressure reaction conditions are that the pressure is increased to 1GPa, then the temperature is increased to 700 ℃, the pressure is maintained, the temperature is kept for 1h, and then quenching is performed;
step 4, after the high-temperature high-pressure reaction is finished, taking out a cylindrical sample wrapped by platinum, cutting a platinum pipe by using a diamond cutter, taking out the sample, and using fine sand paper to vertically move the sampleGrinding off KCl layer to obtain iron doped titanium oxide (Ti 0.95 Fe 0.05 )O 2-δ No other impurities.
Example 2:
high temperature high pressure Cheng Tie doped titanium oxide (Ti) 0.9 Fe 0.1 )O 2-δ Comprising the following steps:
step 1, use of analytically pure TiOTiO 2 And analytically pure iron oxide Fe 2 O 3 Uniformly mixing and grinding the mixture according to a molar ratio of 18:1 to serve as a starting raw material;
step 2, placing the mixture powder into a phi 6 grinding tool by using a powder tablet press to be pressed into a phi 6 multiplied by 5mm cylinder; analytically pure potassium perchlorate KClO 4 Placing the powder into a phi 6 grinding tool to form a phi 6 multiplied by 2mm wafer, and adding KClO 4 Wafer-mixture cylinder-KClO 4 The wafers are sequentially stacked and put into a platinum snap fastener with the inner diameter phi of 6mm and the thickness of 0.1mm for sealing, KClO 4 Providing 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, the h-BN tube with the sample in the step 2 is assembled in a high-pressure assembling block and placed in a hexahedral large press for high-temperature and high-pressure reaction, the high-temperature and high-pressure reaction condition is that the pressure is increased to 2GPa, then the temperature is increased to 750 ℃, and the quenching is performed after the pressure maintaining and heat preserving for 1 hour;
step 4, after the high-temperature high-pressure reaction is finished, taking out a cylindrical sample wrapped by platinum, cutting a platinum tube by using a diamond cutter, taking out the sample, and polishing KCl layers on the upper and lower sides of the sample by using fine sand paper to obtain iron-doped titanium oxide (Ti 0.9 Fe 0.1 )O 2-δ No other impurities.
Example 3:
high temperature high pressure Cheng Tie doped titanium oxide (Ti) 0.85 Fe 0.15 )O 2-δ Comprising the following steps:
step 1, use of analytically pure TiOTiO 2 And analytically pure iron oxide Fe 2 O 3 Uniformly mixing and grinding the raw materials in a molar ratio of 34:3 to obtain a starting material;
step 2, using a powder tablet press to powder the mixturePressing the powder into a cylinder with the diameter of phi 6 multiplied by 5mm in a phi 6 grinding tool; analytically pure potassium perchlorate KClO 4 Placing the powder into a phi 6 grinding tool to form a phi 6 multiplied by 2mm wafer, and adding KClO 4 Wafer-mixture cylinder-KClO 4 The wafers are sequentially stacked and put into a platinum snap fastener with the inner diameter phi of 6mm and the thickness of 0.1mm for sealing, KClO 4 Providing 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 tube with the sample in the step 2 in a high-pressure assembling block, placing the h-BN tube in a hexahedral top large-pressure machine 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 quenching is performed after the pressure maintaining and heat preserving for 1 hour;
step 4, after the high-temperature high-pressure reaction is finished, taking out a cylindrical sample wrapped by platinum, cutting a platinum tube by using a diamond cutter, taking out the sample, and polishing KCl layers on the upper and lower sides of the sample by using fine sand paper to obtain iron-doped titanium oxide (Ti 0.85 Fe 0.15 )O 2-δ . No other impurities.
Comparative examples:
step 1, use of analytically pure TiOTiO 2 And analytically pure iron oxide Fe 2 O 3 Uniformly mixing and grinding the raw materials in a molar ratio of 8:1 to obtain a starting raw material;
step 2, placing the mixture powder into a phi 6 grinding tool by using a powder tablet press to be pressed into a phi 6 multiplied by 5mm cylinder; analytically pure potassium perchlorate KClO 4 Placing the powder into a phi 6 grinding tool to form a phi 6 multiplied by 2mm wafer, and adding KClO 4 Wafer-mixture cylinder-KClO 4 The wafers are sequentially stacked and put into a platinum snap fastener with the inner diameter phi of 6mm and the thickness of 0.1mm for sealing, KClO 4 Providing 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, the h-BN tube with the sample in the step 2 is assembled in a high-pressure assembling block and placed in a hexahedral large press for high-temperature and high-pressure reaction, the high-temperature and high-pressure reaction condition is that the pressure is increased to 2GPa, then the temperature is increased to 750 ℃, and the quenching is performed after the pressure maintaining and heat preserving for 1 hour;
step 4, after the high-temperature high-pressure reaction is completed, the platinum-coated cylinder is coated with platinumTaking out the sample, cutting the platinum tube by using a diamond cutter, taking out the sample, and grinding the KCl layers on the upper and lower sides of the sample by using fine sand paper to obtain products of iron-doped titanium oxide and iron titanate Fe 3 TiO 5 And (3) mixing phases.
In addition, the h-BN tubes described in examples 1 to 3 and comparative examples were specifically operated as follows: and (3) drilling a Kong Zuocheng h-BN pipe with the diameter of 6mm at the center of an h-BN rod with the diameter of 10mm on a lathe, plugging a sample into the pipe, sealing the two ends by h-BN sheets with the thickness of 2mm with the diameter of 6mm, and particularly, the method for assembling the h-BN pipe in a high-pressure synthesis assembly block comprises the following steps of: selecting a pyrophyllite block, and punching a circular through hole with the diameter of 12mm in the center of the pyrophyllite block; a circular graphite heating furnace with the outer diameter of 12mm and the inner diameter phi of 10mm is sleeved in the circular through hole; placing a sample sealed by an h-BN tube with the thickness of 10mm in the middle of a graphite heating furnace; and sealing the upper end and the lower end of the round graphite heating furnace by using pyrophyllite plugs.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (4)
1. A method for doping titanium oxide by high temperature and high pressure Cheng Tie, which is characterized by comprising the following steps:
step 1, use of analytically pure TiOx TiO 2 And analytically pure iron oxide Fe 2 O 3 In a molar ratio [2 (1-x)]X is the doping amount of iron, 0<x≤0.15；
Step 2, placing the mixture powder into a phi 6 grinding tool by using a powder tablet press to be pressed into a phi 6 multiplied by 5mm cylinder; analytically pure potassium perchlorate KClO 4 Placing the powder into a phi 6 grinding tool to form a phi 6 multiplied by 2mm wafer, and adding KClO 4 Wafer-mixture cylinder-KClO 4 The 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, a sealed platinum cylinder is arranged in an h-BN tube, and the h-BN is used as a pressure transmission medium;
step 3, the h-BN tube with the sample in the step 2 is assembled in a high-pressure assembling block and placed in a hexahedral top large press for high-temperature high-pressure reaction; the high-temperature high-pressure reaction condition is that the pressure is increased to 1-3GPa, then the temperature is increased to 700-800 ℃, and the quenching is carried out after the pressure maintaining and the heat preserving for 1 hour;
step 4, after the high-temperature high-pressure reaction is finished, taking out a cylindrical sample wrapped by platinum, cutting a platinum tube by using a diamond cutter, taking out the sample, and polishing KCl layers on the upper and lower sides of the sample by using fine sand paper to obtain iron-doped titanium oxide (Ti 1-x Fe x )O 2-δ Delta is the oxygen deficiency.
2. The method according to claim 1, wherein the iron-doped titanium oxide (Ti 1-x Fe x )O 2-δ Is single phase and has no other impurity.
3. The iron-doped titanium oxide obtained according to the method of claim 1, wherein the iron-doped titanium oxide sample is a gray powder, and is deepened as the content of doped iron increases.
4. The iron-doped titanium oxide obtained according to claim 1, wherein the iron-doped titanium oxide sample is of the formula (Ti 1-x Fe x )O 2-δ ，0<x is less than or equal to 0.15, no other impurities exist, the crystal structure is tetragonal, the space group is P42/mn, the lattice parameter a=4-5A and c=2-3A.
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| CN202111486635.3A CN114162856B (en) | 2021-12-07 | 2021-12-07 | Method for doping titanium oxide by using Cheng Tie under high temperature and high pressure |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1036593A1 (en) * | 1999-03-16 | 2000-09-20 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Titanium dioxide photocatalyst with Fe3+ ions added thereon |
| CN103601238A (en) * | 2013-11-07 | 2014-02-26 | 昆明理工大学 | Method for preparing iron-doped TiO2 powder through microwave solid-phase reaction |
| CN104844162A (en) * | 2015-04-08 | 2015-08-19 | 中国科学院物理研究所 | High-temperature ferrimagnetic semiconductor CaCu3Fe2Os2O12 and preparation method thereof |
| CN105536792A (en) * | 2015-11-30 | 2016-05-04 | 华南理工大学 | Iron-doped titanium dioxide powder preparation method |
| CN108275719A (en) * | 2018-01-30 | 2018-07-13 | 北京工业大学 | A kind of TiO that Phase Proportion is controllable2The preparation and application of heterojunction material |
| CN111229223A (en) * | 2020-01-19 | 2020-06-05 | 中国石油大学(北京) | Iron oxide doped mixed crystal titanium dioxide nano-net photocatalytic composite material |
| CN112851351A (en) * | 2020-08-29 | 2021-05-28 | 中国科学院地球化学研究所 | Method for directly synthesizing iron-doped zinc sulfide block through solid-phase reaction |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5498009B2 (en) * | 2008-10-30 | 2014-05-21 | 国立大学法人 東京大学 | Photocatalyst material, organic matter decomposition method, interior member, air cleaning device, oxidizer manufacturing device |
| US10413888B2 (en) * | 2016-10-04 | 2019-09-17 | Rh-Imaging Systems, Inc. | Iron doped titanium dioxide nanocrystals and their use as photocatalysts |
-
2021
- 2021-12-07 CN CN202111486635.3A patent/CN114162856B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1036593A1 (en) * | 1999-03-16 | 2000-09-20 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Titanium dioxide photocatalyst with Fe3+ ions added thereon |
| CN103601238A (en) * | 2013-11-07 | 2014-02-26 | 昆明理工大学 | Method for preparing iron-doped TiO2 powder through microwave solid-phase reaction |
| CN104844162A (en) * | 2015-04-08 | 2015-08-19 | 中国科学院物理研究所 | High-temperature ferrimagnetic semiconductor CaCu3Fe2Os2O12 and preparation method thereof |
| CN105536792A (en) * | 2015-11-30 | 2016-05-04 | 华南理工大学 | Iron-doped titanium dioxide powder preparation method |
| CN108275719A (en) * | 2018-01-30 | 2018-07-13 | 北京工业大学 | A kind of TiO that Phase Proportion is controllable2The preparation and application of heterojunction material |
| CN111229223A (en) * | 2020-01-19 | 2020-06-05 | 中国石油大学(北京) | Iron oxide doped mixed crystal titanium dioxide nano-net photocatalytic composite material |
| CN112851351A (en) * | 2020-08-29 | 2021-05-28 | 中国科学院地球化学研究所 | Method for directly synthesizing iron-doped zinc sulfide block through solid-phase reaction |
Non-Patent Citations (4)
| Title |
|---|
| Electronic structure of Ti1−xFexO2−δ thin films with oxygen vacancies probed by soft X-ray spectroscopy;Katsuya Usui;Japanese Journal of Applied Physics;第54卷(第6S1期);06FJ07 * |
| Highly dispersed titania-supported iron oxide catalysts for efficient heterogeneous photo-Fenton oxidation: Influencing factors, synergistic effects and mechanism insight;Yadong Zhang;Journal of Colloid and Interface Science;第587卷;467-478 * |
| 掺铁二氧化钛纳米晶的制备及其光催化性能;钟敏;韦之豪;司平占;李红;卫国英;葛洪良;韩高荣;;硅酸盐学报(第01期);全文 * |
| 掺铁纳米TiO_2光催化氧化SO_2的研究;周文;陈凡植;李冠文;王军;;能源环境保护(第01期);全文 * |
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