CN111036210A - (001) Surface exposed-three-dimensional laminated structure TiO2Preparation method of/nano-iron composite catalyst - Google Patents
(001) Surface exposed-three-dimensional laminated structure TiO2Preparation method of/nano-iron composite catalyst Download PDFInfo
- Publication number
- CN111036210A CN111036210A CN201911352420.5A CN201911352420A CN111036210A CN 111036210 A CN111036210 A CN 111036210A CN 201911352420 A CN201911352420 A CN 201911352420A CN 111036210 A CN111036210 A CN 111036210A
- Authority
- CN
- China
- Prior art keywords
- nano
- laminated structure
- dimensional laminated
- tio
- iron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 76
- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000002245 particle Substances 0.000 claims abstract description 38
- 238000002360 preparation method Methods 0.000 claims abstract description 35
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims abstract description 28
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 claims abstract description 22
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000013078 crystal Substances 0.000 claims abstract description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000000694 effects Effects 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 12
- 238000005054 agglomeration Methods 0.000 claims abstract description 7
- 230000002776 aggregation Effects 0.000 claims abstract description 7
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000002244 precipitate Substances 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 239000012153 distilled water Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 230000001376 precipitating effect Effects 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims description 10
- 239000010935 stainless steel Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 238000003475 lamination Methods 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 2
- 230000002401 inhibitory effect Effects 0.000 claims description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 230000004298 light response Effects 0.000 abstract description 3
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 238000013032 photocatalytic reaction Methods 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 3
- 239000010936 titanium Substances 0.000 abstract description 3
- 229910052719 titanium Inorganic materials 0.000 abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 abstract description 2
- 238000005137 deposition process Methods 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 abstract 1
- 238000011068 loading method Methods 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 238000011160 research Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910001959 inorganic nitrate Inorganic materials 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
Images
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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B01J35/39—
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention provides a (001) surface exposed-three-dimensional laminated structure TiO2The preparation method of the/nano-iron composite catalyst comprises a two-step hydrothermal method and a one-step liquid-phase reduction deposition method. The invention takes titanium tetrafluoride as a titanium source, isobutanol, isopropanol and hydrofluoric acid as structure control agents and NaBH4Or KBH4Is a reducing agent. Firstly, a two-step hydrothermal method is adopted to prepare (001) surface exposed-three-dimensional laminated structure TiO2Catalyst, and one-step liquid phase reduction deposition process to deposit nanometer iron particle on TiO2On the (001) surface of the substrate to prepare a (001) surface exposed-three-dimensional laminated structure TiO2A nano-iron composite catalyst. The lamellar structure of the catalyst not only effectively increases the exposure proportion of a high-activity (001) crystal face and the specific surface area of a material, but also effectively improves the stability and the oxidation resistance of nano iron in the air by the three-dimensional laminated structure in a nano iron composite state, so that nano iron particles are more refined and uniform, and the nano iron particles are greatly inhibitedThe agglomeration effect of the nano iron material increases the active sites of the nano iron material. And, in the course of photocatalytic reaction, nano iron and TiO2The mutual synergistic effect can not only compensate the consumption of the nano iron, but also effectively accelerate the electron transfer rate, promote the separation of photo-generated electrons and holes and the generation of hydroxyl free radicals, enhance the photoelectric effect and expand the visible light response range.
Description
Technical Field
The invention relates to an inorganic functional material and a fine chemical preparation technology, in particular to a (001) surface exposed-three-dimensional laminated structure TiO2A preparation method of a nano-iron composite catalyst.
Background
It is well known that among the numerous inorganic semiconductor materials, TiO2Has the advantages of moderate band gap position, simple synthesis process, no harm to environment and human body, stable chemical property, light resistance, acid and alkali corrosion resistance and the likeHave been studied intensively for a long time and have been widely used in the fields of photocatalysis, solar cells, water splitting, sensor design, and the like. However, nano TiO2The crystal grains have the characteristics of low utilization rate of visible light, easy recombination of photo-generated electrons and holes, and easy agglomeration and inactivation at a nanoscale scale. Therefore, scholars at home and abroad aim at the nano TiO2The defects of crystal grains develop a series of researches on auxiliary modification and reconstruction of self-morphology structure. In 2008, Yang et al firstly synthesized micron-sized anatase TiO with 47% exposed (001) crystal face proportion by using hydrofluoric acid (HF) as a crystal face control agent through a hydrothermal method2Single crystal, the material shows TiO of (101) crystal face exposed than conventional2Has higher photocatalytic activity. Subsequently, against the exposed anatase TiO of the (001) face2The research of single crystal is remarkably focused, and TiO with higher (001) face exposure ratio is synthesized on the basis of the single crystal2Nanosheets. However, TiO2The nano-sheet generally has the defects of easy agglomeration, volatile electrons and poor dispersibility; therefore, researchers at home and abroad adopt different titanium sources and an improved synthesis method to realize the purpose of exposing (001) surface TiO2Self-assembly of single crystal wafers, some from (001) plane TiO2TiO with spherical, flower-like and other multilevel structure formed by self-assembly of single crystal wafer2The catalyst is synthesized successively; the self-assembly structure of the single chip can effectively improve the transmission efficiency of photoproduction electrons and promote the separation of photoproduction electrons and holes, thereby leading TiO to2The photocatalytic activity and the photoelectric effect of the photocatalyst are greatly improved.
As a new environment restoration engineering material, the nano-iron has the characteristics of large specific surface area, high chemical reaction activity, excellent surface property, high removal efficiency on a plurality of pollutants difficult to biodegrade and the like, and is widely concerned and applied in the field of environment restoration and treatment. To date, nano-iron has been shown to be effective in removing a variety of contaminants, including nitroaromatics, organic halides, inorganic nitrates, polycyclic aromatic hydrocarbons, organic dyes, a variety of heavy metals, and antibiotic drugs. However, the high activity of nano-iron itself makes it extremely poor in stability in air, and it is very easy to be oxidized or even spontaneously combusted after contacting with oxygen, and due to its nano-size, it is easy to agglomerate, and the dispersibility in aqueous media is poor, thus limiting the application of nano-iron materials in practical water treatment processes. Researches suggest that the composite nano-iron material which can be stably maintained in the air and has good aqueous medium dispersibility and separability is prepared by loading nano-iron on a carrier with larger size and stable property, and has important practical significance and application value for promoting the application of the nano-iron in environmental remediation.
Research shows that the nano iron/TiO2The photocatalysis technology is TiO for improving visible light catalytic activity and promoting photoproduction electron-hole separation2And (3) modification technology. In the process of photocatalytic reaction, nano iron and TiO2The mutual synergistic effect can not only compensate the consumption of the nano iron, but also improve the agglomeration effect of the nano iron; but also can effectively accelerate the electron transfer rate, promote the separation of photogenerated electrons and holes and the generation of hydroxyl free radicals, enhance the photoelectric effect and expand the visible light response range.
Disclosure of Invention
The invention aims to provide a (001) surface exposed-three-dimensional laminated structure TiO2A preparation method of a nano-iron composite catalyst. The invention takes titanium tetrafluoride as a titanium source, isobutanol, isopropanol and hydrofluoric acid as structure control agents and NaBH4Or KBH4Is a reducing agent. Firstly, a two-step hydrothermal method is adopted to prepare (001) surface exposed-three-dimensional laminated structure TiO2Catalyst, and one-step liquid phase reduction deposition process to deposit nanometer iron particle on TiO2On the (001) surface of the substrate to prepare a (001) surface exposed-three-dimensional laminated structure TiO2A nano-iron composite catalyst. The lamellar structure of the catalyst not only effectively increases the exposure proportion of a high-activity (001) crystal face and the specific surface area of a material, but also effectively improves the stability and the oxidation resistance of nano iron in air by the three-dimensional laminated structure in a nano iron composite state, so that nano iron particles are more refined and uniform, and the agglomeration effect of the nano iron particles is greatly inhibited. And, in the course of photocatalytic reaction, nano iron and TiO2The mutual synergistic effect can not only compensate the nanometerThe consumption of iron can effectively accelerate the electron transfer rate, promote the separation of photogenerated electrons and holes and the generation of hydroxyl radicals, enhance the photoelectric effect and expand the visible light response range.
In order to achieve the aim, the invention adopts the technical scheme that a (001) surface exposed-three-dimensional laminated structure TiO is provided2The preparation method of the/nano-iron composite catalyst comprises the following steps:
(1) preparation of titanium tetrafluoride solution
4.956g of titanium tetrafluoride is dissolved in 1L of hydrochloric acid solution with the concentration of 2mol/L at the temperature of 15-35 ℃ to obtain titanium tetrafluoride solution with the pH = 2 and the concentration of 0.04 mol/L;
（2）TiO2preparation of the nuclei
50ml to 60ml of 0.04mol/L titanium tetrafluoride solution and 10 ml to 20 ml of isobutanol are placed in a beaker to be magnetically stirred for 1 hour, and are added into a 100ml of polytetrafluoroethylene-lined stainless steel high-pressure reaction kettle after being fully mixed; placing in a muffle furnace, keeping the temperature at 180 ℃ for 6-8 h, cooling, precipitating, filtering to obtain white solid particles, washing with distilled water for 3-5 times, centrifuging, and drying to obtain a sample X;
(3) (001) plane exposed-three-dimensional laminated structure TiO2Preparation of the catalyst
Placing 1g-3g of sample X, 10 ml-20 ml of isobutanol, 10 ml-20 ml of isopropanol and 0.05ml-0.2ml of hydrofluoric acid (mass fraction is 40%) in a beaker, magnetically stirring for 0.5h, fully mixing, and adding into a 50ml of polytetrafluoroethylene-lined stainless steel high-pressure reaction kettle; placing in a muffle furnace, keeping the temperature at 200 ℃ for 15-20 h, cooling, precipitating, filtering to obtain white solid particles, washing with distilled water for 3-5 times, centrifuging, and drying to obtain sample Y;
and (3) removing fluorine on crystal faces: calcining the prepared sample Y in a muffle furnace at 500 ℃ for 90-100 min, cooling, washing with 0.1mol/L NaOH solution for 3-5 times, and washing with distilled water for 3-5 times to obtain (001) surface exposed-three-dimensional laminated structure TiO2The catalyst is protected by nitrogen and is stored in a sealed way under the anaerobic condition;
(4) (001) face exposed-three dimensional laminate structureTiO2Preparation of/nano-iron composite catalyst
0.5g to 2.0g of the above-prepared (001) plane-exposed three-dimensional laminated structure TiO2Catalyst, 50ml of absolute ethyl alcohol and 100ml of FeSO with the concentration of 0.2mol/L-0.8mol/L4·7H2Placing the O aqueous solution in a three-neck flask, sealing and marking as a component A; placing the component A on a magnetic stirrer, introducing nitrogen into a three-neck flask for 10min for protection, starting magnetic stirring, and ultrasonically dispersing the component A for 30min-50min to uniformly mix the component A; after 30min, standing and precipitating the component A for 20min, removing supernatant, performing centrifugal separation to obtain solid precipitate, performing vacuum drying on the solid precipitate to obtain a sample M, and performing nitrogen protection and sealed storage under an oxygen-free condition for later use;
100ml of NaBH with the concentration of 0.4mol/L is prepared4Or KBH4Adjusting pH of the solution to 9-10 with NaOH to obtain weakly alkaline NaBH4Or KBH4A solution, labeled as component B;
placing the sample M and 60ml of absolute ethyl alcohol into a three-neck flask, sealing and placing the three-neck flask on a magnetic stirrer, and then uniformly mixing the sample M and the absolute ethyl alcohol under the protection of nitrogen atmosphere, wherein the sample M is marked as a component C; dropwise adding the prepared component B into the component C at a speed of 45-60 drops/min, continuously stirring and protecting with nitrogen for 40min after dropwise adding, standing for 30min, filtering to obtain black precipitate particles, washing the black precipitate particles with absolute ethanol for 3-5 times, and drying the washed black precipitate particles in a vacuum drying oven for 3-5 h to obtain the black (001) surface exposed-three-dimensional laminated structure TiO component2The/nano-iron composite catalyst is protected by nitrogen and is stored in a sealed way under the anaerobic condition.
The invention has the following effects: 1. the (001) surface exposed-three-dimensional laminated structure TiO of the invention2On the basis of keeping the high activity of the nano-iron, the nano-iron composite catalyst disperses the nano-iron particles on the (001) surface sheet layer structure, thereby not only improving the stability and the oxidation resistance of the nano-iron composite catalyst in the air, but also greatly inhibiting the agglomeration effect of the nano-iron and increasing the active sites of the nano-iron. Meanwhile, the specific three-dimensional lamination structure increases the exposure proportion of the (001) surface and increasesThe specific surface area of the material is shown.
2. The (001) surface exposed-three-dimensional laminated structure TiO of the invention2Nano iron particles in/nano iron composite catalyst react with TiO in photocatalysis2The synergistic effect can not only compensate the consumption of nano iron, but also promote the separation of photo-generated electrons and holes and enhance TiO2Photoelectric effect of single crystal, extended TiO2The spectrum response range of the photocatalyst promotes the generation of more hydroxyl radicals and improves the photocatalytic activity.
3. The (001) surface exposed-three-dimensional laminated structure TiO of the invention2The preparation method of the catalyst adopts a two-step hydrothermal method, and the (001) surface exposure-three-dimensional lamination structure is prepared by effectively controlling the action characteristics of hydrofluoric acid, isobutanol and isopropanol on crystal surfaces and two different hydrothermal conditions, and the thickness of a single piece is 30-90 nm.
4. The (001) surface exposed-three-dimensional laminated structure TiO of the invention2The grain diameter range of the/nano-iron composite catalyst is 6-10 mu m, and the specific surface area is 480 m2/g-560 m2The grain diameter of the nano iron particles compounded on the (001) surface is 200 nm-400 nm.
Drawings
FIG. 1 shows a (001) plane exposed-three-dimensional laminated structure TiO of the present invention2SEM image of/nano-iron composite catalyst.
Detailed Description
(001) face exposed-three dimensional laminated structures TiO of the invention in combination with the following examples2The preparation method of the/nano-iron composite catalyst is illustrated.
Example 1 (001) plane exposed-three dimensional laminated structure TiO with 30% nano-iron loading2Preparation of/nano-iron composite catalyst
(1) Preparation of titanium tetrafluoride solution
4.956g of titanium tetrafluoride is dissolved in 1L of hydrochloric acid solution with the concentration of 2mol/L at the temperature of 15-35 ℃ to obtain titanium tetrafluoride solution with the pH = 2 and the concentration of 0.04 mol/L;
（2）TiO2preparation of the nuclei
Putting 60ml of 0.04mol/L titanium tetrafluoride solution and 10 ml of isobutanol in a beaker, magnetically stirring for 1 hour, fully mixing, and adding into a 100ml of polytetrafluoroethylene-lined stainless steel high-pressure reaction kettle; placing in a muffle furnace, keeping the temperature at 180 ℃ for 6h, cooling, precipitating, filtering to obtain white solid particles, washing with distilled water for 5 times, centrifuging, and drying to obtain a sample X;
(3) (001) plane exposed-three-dimensional laminated structure TiO2Preparation of the catalyst
Placing 3g of sample X, 20 ml of isobutanol, 20 ml of isopropanol and 0.05ml of hydrofluoric acid (mass fraction is 40%) in a beaker, magnetically stirring for 0.5h, fully mixing, and adding into a 50ml of polytetrafluoroethylene-lined stainless steel high-pressure reaction kettle; placing the mixture in a muffle furnace, keeping the temperature at 200 ℃ for 15h, cooling, precipitating and filtering to obtain white solid particles, washing the white solid particles for 3 times by using distilled water, and performing centrifugal separation and drying to obtain a sample Y;
and (3) removing fluorine on crystal faces: calcining the prepared sample Y in a muffle furnace at 500 ℃ for 90-100 min, cooling, washing with 0.1mol/L NaOH solution for 5 times, washing with distilled water for 3 times to obtain (001) surface exposed-three-dimensional laminated structure TiO2The catalyst is protected by nitrogen and is stored in a sealed way under the anaerobic condition;
(4) (001) plane exposed-three-dimensional laminated structure TiO2Preparation of/nano-iron composite catalyst
2.0g of the prepared (001) face-exposed-three-dimensional laminated structure TiO2Catalyst, 50ml of absolute ethyl alcohol and 100ml of FeSO with the concentration of 0.2mol/L4·7H2Placing the O aqueous solution in a three-neck flask, sealing and marking as a component A; placing the component A on a magnetic stirrer, introducing nitrogen into a three-neck flask for 10min for protection, starting magnetic stirring, and carrying out ultrasonic dispersion on the component A for 30min to uniformly mix the component A; after 30min, standing and precipitating the component A for 20min, removing supernatant, performing centrifugal separation to obtain solid precipitate, performing vacuum drying on the solid precipitate to obtain a sample M, and performing nitrogen protection and sealed storage under an oxygen-free condition for later use;
100ml of NaBH with the concentration of 0.4mol/L is prepared4Or KBH4Adjusting pH of the solution to 9 with NaOH to obtainWeakly basic NaBH4Or KBH4A solution, labeled as component B;
placing the sample M and 60ml of absolute ethyl alcohol into a three-neck flask, sealing and placing the three-neck flask on a magnetic stirrer, and then uniformly mixing the sample M and the absolute ethyl alcohol under the protection of nitrogen atmosphere, wherein the sample M is marked as a component C; dropwise adding the prepared component B into the component C at a dropping speed of 60 drops/min, continuously stirring and protecting with nitrogen for 40min after the dropwise adding is finished, standing for 30min, filtering to obtain black precipitated particles, washing the black precipitated particles with absolute ethyl alcohol for 5 times, and drying the washed black precipitated particles in a vacuum drying oven for 3h to obtain the black (001) surface exposed-three-dimensional laminated structure TiO with the nano-iron loading of 30%2The/nano-iron composite catalyst is protected by nitrogen and is stored in a sealed way under the anaerobic condition.
Example 2 (001) plane exposed-three dimensional laminated structure TiO with 60% nano-iron loading2Preparation of/nano-iron composite catalyst
(1) Preparation of titanium tetrafluoride solution
4.956g of titanium tetrafluoride is dissolved in 1L of hydrochloric acid solution with the concentration of 2mol/L at the temperature of 15-35 ℃ to obtain titanium tetrafluoride solution with the pH = 2 and the concentration of 0.04 mol/L;
（2）TiO2preparation of the nuclei
Putting 60ml of 0.04mol/L titanium tetrafluoride solution and 20 ml of isobutanol in a beaker, magnetically stirring for 1 hour, fully mixing, and adding into a 100ml of polytetrafluoroethylene-lined stainless steel high-pressure reaction kettle; placing in a muffle furnace, keeping the temperature at 180 ℃ for 8h, cooling, precipitating, filtering to obtain white solid particles, washing with distilled water for 5 times, centrifuging, and drying to obtain a sample X;
(3) (001) plane exposed-three-dimensional laminated structure TiO2Preparation of the catalyst
2g of sample X, 20 ml of isobutanol, 20 ml of isopropanol and 0.1ml of hydrofluoric acid (mass fraction is 40%) are placed in a beaker and magnetically stirred for 0.5h, and after full mixing, the mixture is added into a 50ml of polytetrafluoroethylene-lined stainless steel high-pressure reaction kettle; placing in a muffle furnace, keeping the temperature at 200 ℃ for 18h, cooling, precipitating, filtering to obtain white solid particles, washing with distilled water for 5 times, centrifuging, and drying to obtain a sample Y;
and (3) removing fluorine on crystal faces: calcining the prepared sample Y in a muffle furnace at 500 ℃ for 90 min, cooling, washing with 0.1mol/L NaOH solution for 5 times, washing with distilled water for 5 times to obtain (001) surface exposed-three-dimensional laminated structure TiO2The catalyst is protected by nitrogen and is stored in a sealed way under the anaerobic condition;
(4) (001) plane exposed-three-dimensional laminated structure TiO2Preparation of/nano-iron composite catalyst
1.0g of the (001) plane-exposed three-dimensional laminated structure TiO prepared above2Catalyst, 50ml of absolute ethyl alcohol and 100ml of FeSO with the concentration of 0.5mol/L4·7H2Placing the O aqueous solution in a three-neck flask, sealing and marking as a component A; placing the component A on a magnetic stirrer, introducing nitrogen into a three-neck flask for 10min for protection, starting magnetic stirring, and ultrasonically dispersing the component A for 30min-50min to uniformly mix the component A; after 30min, standing and precipitating the component A for 20min, removing supernatant, performing centrifugal separation to obtain solid precipitate, performing vacuum drying on the solid precipitate to obtain a sample M, and performing nitrogen protection and sealed storage under an oxygen-free condition for later use;
100ml of NaBH with the concentration of 0.4mol/L is prepared4Or KBH4The solution is adjusted to pH 10 by NaOH to prepare alkalescent NaBH4Or KBH4A solution, labeled as component B;
placing the sample M and 60ml of absolute ethyl alcohol into a three-neck flask, sealing and placing the three-neck flask on a magnetic stirrer, and then uniformly mixing the sample M and the absolute ethyl alcohol under the protection of nitrogen atmosphere, wherein the sample M is marked as a component C; dropwise adding the prepared component B into the component C at a speed of 50 drops/min, continuously stirring and protecting with nitrogen for 40min after dropwise adding is finished, standing for 30min, filtering to obtain black precipitated particles, washing the black precipitated particles with absolute ethyl alcohol for 5 times, and drying the washed black precipitated particles in a vacuum drying oven for 5 hours to obtain the black (001) surface exposed-three-dimensional laminated structure TiO2The/nano-iron composite catalyst is protected by nitrogen and is stored in a sealed way under the anaerobic condition.
Example 3 nanometer iron negative(001) plane exposed-three-dimensional laminated structure TiO with loading of 90%2Preparation of/nano-iron composite catalyst
(1) Preparation of titanium tetrafluoride solution
4.956g of titanium tetrafluoride is dissolved in 1L of hydrochloric acid solution with the concentration of 2mol/L at the temperature of 15-35 ℃ to obtain titanium tetrafluoride solution with the pH = 2 and the concentration of 0.04 mol/L;
（2）TiO2preparation of the nuclei
50ml of 0.04mol/L titanium tetrafluoride solution and 20 ml of isobutanol are placed in a beaker to be magnetically stirred for 1 hour, and are added into a 100ml of polytetrafluoroethylene-lined stainless steel high-pressure reaction kettle after being fully mixed; placing in a muffle furnace, keeping the temperature at 180 ℃ for 8h, cooling, precipitating, filtering to obtain white solid particles, washing with distilled water for 5 times, centrifuging, and drying to obtain a sample X;
(3) (001) plane exposed-three-dimensional laminated structure TiO2Preparation of the catalyst
2g of sample X, 20 ml of isobutanol, 20 ml of isopropanol and 0.1ml of hydrofluoric acid (mass fraction is 40%) are placed in a beaker and magnetically stirred for 0.5h, and after full mixing, the mixture is added into a 50ml of polytetrafluoroethylene-lined stainless steel high-pressure reaction kettle; placing in a muffle furnace, keeping the temperature at 200 ℃ for 16h, cooling, precipitating, filtering to obtain white solid particles, washing with distilled water for 5 times, centrifuging, and drying to obtain a sample Y;
and (3) removing fluorine on crystal faces: calcining the prepared sample Y in a muffle furnace at 500 ℃ for 90 min, cooling, washing with 0.1mol/L NaOH solution for 5 times, washing with distilled water for 5 times to obtain (001) surface exposed-three-dimensional laminated structure TiO2The catalyst is protected by nitrogen and is stored in a sealed way under the anaerobic condition;
(4) (001) plane exposed-three-dimensional laminated structure TiO2Preparation of/nano-iron composite catalyst
2.0g of the prepared (001) face-exposed-three-dimensional laminated structure TiO2Catalyst, 50ml of absolute ethyl alcohol and 100ml of FeSO with the concentration of 0.8mol/L4·7H2Placing the O aqueous solution in a three-neck flask, sealing and marking as a component A; placing the component A on a magnetic stirrer in the first directionIntroducing nitrogen into the three-neck flask for 10min for protection, starting magnetic stirring, and ultrasonically dispersing the component A for 50min to uniformly mix the component A; after 30min, standing and precipitating the component A for 20min, removing supernatant, performing centrifugal separation to obtain solid precipitate, performing vacuum drying on the solid precipitate to obtain a sample M, and performing nitrogen protection and sealed storage under an oxygen-free condition for later use;
100ml of NaBH with the concentration of 0.4mol/L is prepared4Or KBH4The solution is adjusted to pH 10 by NaOH to prepare alkalescent NaBH4Or KBH4A solution, labeled as component B;
placing the sample M and 60ml of absolute ethyl alcohol into a three-neck flask, sealing and placing the three-neck flask on a magnetic stirrer, and then uniformly mixing the sample M and the absolute ethyl alcohol under the protection of nitrogen atmosphere, wherein the sample M is marked as a component C; dropwise adding the prepared component B into the component C at a speed of 60 drops/min, continuously stirring and protecting with nitrogen for 40min after dropwise adding is finished, standing for 30min, filtering to obtain black precipitated particles, washing the black precipitated particles with absolute ethyl alcohol for 5 times, and drying the washed black precipitated particles in a vacuum drying oven for 5 hours to obtain the black (001) surface exposed-three-dimensional laminated structure TiO2The/nano-iron composite catalyst is protected by nitrogen and is stored in a sealed way under the anaerobic condition.
Claims (5)
1. (001) surface exposed-three-dimensional laminated structure TiO2The preparation method of the/nano-iron composite catalyst comprises the following steps:
(1) preparation of titanium tetrafluoride solution
4.956g of titanium tetrafluoride is dissolved in 1L of hydrochloric acid solution with the concentration of 2mol/L at the temperature of 15-35 ℃ to obtain titanium tetrafluoride solution with the pH = 2 and the concentration of 0.04 mol/L;
（2）TiO2preparation of the nuclei
50ml to 60ml of 0.04mol/L titanium tetrafluoride solution and 10 ml to 20 ml of isobutanol are placed in a beaker to be magnetically stirred for 1 hour, and are added into a 100ml of polytetrafluoroethylene-lined stainless steel high-pressure reaction kettle after being fully mixed; placing in a muffle furnace, keeping the temperature at 180 ℃ for 6-8 h, cooling, precipitating, filtering to obtain white solid particles, washing with distilled water for 3-5 times, centrifuging, and drying to obtain a sample X;
(3) (001) plane exposed-three-dimensional laminated structure TiO2Preparation of the catalyst
Placing 1g-3g of sample X, 10 ml-20 ml of isobutanol, 10 ml-20 ml of isopropanol and 0.05ml-0.2ml of hydrofluoric acid (mass fraction is 40%) in a beaker, magnetically stirring for 0.5h, fully mixing, and adding into a 50ml of polytetrafluoroethylene-lined stainless steel high-pressure reaction kettle; placing in a muffle furnace, keeping the temperature at 200 ℃ for 15-20 h, cooling, precipitating, filtering to obtain white solid particles, washing with distilled water for 3-5 times, centrifuging, and drying to obtain sample Y;
and (3) removing fluorine on crystal faces: calcining the prepared sample Y in a muffle furnace at 500 ℃ for 90-100 min, cooling, washing with 0.1mol/L NaOH solution for 3-5 times, and washing with distilled water for 3-5 times to obtain (001) surface exposed-three-dimensional laminated structure TiO2The catalyst is protected by nitrogen and is stored in a sealed way under the anaerobic condition;
(4) (001) plane exposed-three-dimensional laminated structure TiO2Preparation of/nano-iron composite catalyst
0.5g to 2.0g of the above-prepared (001) plane-exposed three-dimensional laminated structure TiO2Catalyst, 50ml of absolute ethyl alcohol and 100ml of FeSO with the concentration of 0.2mol/L-0.8mol/L4·7H2Placing the O aqueous solution in a three-neck flask, sealing and marking as a component A; placing the component A on a magnetic stirrer, introducing nitrogen into a three-neck flask for 10min for protection, starting magnetic stirring, and ultrasonically dispersing the component A for 30min-50min to uniformly mix the component A; after 30min, standing and precipitating the component A for 20min, removing supernatant, performing centrifugal separation to obtain solid precipitate, performing vacuum drying on the solid precipitate to obtain a sample M, and performing nitrogen protection and sealed storage under an oxygen-free condition for later use;
100ml of NaBH with the concentration of 0.4mol/L is prepared4Or KBH4Adjusting pH of the solution to 9-10 with NaOH to obtain weakly alkaline NaBH4Or KBH4A solution, labeled as component B;
the sample M and 60ml of absolute ethyl alcohol are placed in a three-neck flask, sealed and placed on a magnetic stirrer, and thenUniformly mixing under the protection of nitrogen atmosphere, and marking as a component C; dropwise adding the prepared component B into the component C at a speed of 45-60 drops/min, continuously stirring and protecting with nitrogen for 40min after dropwise adding, standing for 30min, filtering to obtain black precipitate particles, washing the black precipitate particles with absolute ethanol for 3-5 times, and drying the washed black precipitate particles in a vacuum drying oven for 3-5 h to obtain the black (001) surface exposed-three-dimensional laminated structure TiO component2The/nano-iron composite catalyst is protected by nitrogen and is stored in a sealed way under the anaerobic condition.
2. (001) plane exposed-three dimensional laminated structure TiO according to claim 12The preparation method of the/nano-iron composite catalyst is characterized by comprising the following steps: the prepared (001) surface exposed-three-dimensional laminated structure TiO2The method of the catalyst is a two-step hydrothermal method, and the action characteristics of hydrofluoric acid, isobutanol and isopropanol on crystal faces are effectively controlled through two different hydrothermal conditions, so that a (001) face exposure-three-dimensional lamination structure is generated.
3. (001) plane exposed-three dimensional laminated structure TiO according to claim 12The preparation method of the/nano-iron composite catalyst is characterized by comprising the following steps: the prepared (001) surface exposed-three-dimensional laminated structure TiO2The surface of the catalyst is a three-dimensional lamination structure with a (001) surface exposed, and the thickness of a single sheet is 30 nm-90 nm.
4. (001) plane exposed-three dimensional laminated structure TiO according to claim 12The preparation method of the/nano-iron composite catalyst is characterized by comprising the following steps: the prepared (001) surface exposed-three-dimensional laminated structure TiO2The (001) surface of the/nano-iron composite catalyst is dispersed with nano-iron particles, thereby effectively inhibiting the agglomeration effect of the nano-iron particles and increasing the active sites of the nano-iron material.
5. (001) plane exposed-three dimensional laminated structure TiO according to claim 12A preparation method of a nano-iron composite catalyst,the method is characterized in that: the prepared (001) surface exposed-three-dimensional laminated structure TiO2The grain diameter range of the/nano-iron composite catalyst is 6-10 mu m, and the specific surface area is 480 m2/g-560 m2The grain diameter of the nano iron particles compounded on the (001) surface is 200 nm-400 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911352420.5A CN111036210B (en) | 2019-12-25 | 2019-12-25 | (001) Surface exposed-three-dimensional laminated structure TiO 2 Preparation method of/nano-iron composite catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911352420.5A CN111036210B (en) | 2019-12-25 | 2019-12-25 | (001) Surface exposed-three-dimensional laminated structure TiO 2 Preparation method of/nano-iron composite catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111036210A true CN111036210A (en) | 2020-04-21 |
| CN111036210B CN111036210B (en) | 2022-09-13 |
Family
ID=70240111
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911352420.5A Active CN111036210B (en) | 2019-12-25 | 2019-12-25 | (001) Surface exposed-three-dimensional laminated structure TiO 2 Preparation method of/nano-iron composite catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111036210B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1145762A1 (en) * | 2000-04-11 | 2001-10-17 | dmc2 Degussa Metals Catalysts Cerdec AG | Process for the preparation of a vanadia SCR-catalyst supported on titania |
| CN101791545A (en) * | 2010-03-02 | 2010-08-04 | 上海师范大学 | Method for preparing (001) surface-exposed micrometer laminar titanium dioxide photocatalyst |
| CN102078805A (en) * | 2010-12-14 | 2011-06-01 | 华东理工大学 | Preparation method of layered titanium dioxide photochemical catalyst |
-
2019
- 2019-12-25 CN CN201911352420.5A patent/CN111036210B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1145762A1 (en) * | 2000-04-11 | 2001-10-17 | dmc2 Degussa Metals Catalysts Cerdec AG | Process for the preparation of a vanadia SCR-catalyst supported on titania |
| CN101791545A (en) * | 2010-03-02 | 2010-08-04 | 上海师范大学 | Method for preparing (001) surface-exposed micrometer laminar titanium dioxide photocatalyst |
| CN102078805A (en) * | 2010-12-14 | 2011-06-01 | 华东理工大学 | Preparation method of layered titanium dioxide photochemical catalyst |
Non-Patent Citations (3)
| Title |
|---|
| LIFEN LIU ETAL.: "Photocatalytic degradation of 2,4-dichlorophenol using nanoscale Fe/TiO2", 《CHEMICAL ENGINEERING JOURNAL》 * |
| WEIWEI SUN ETAL.: "Layer-by-Layer Self-Assembly of TiO2 Hierarchical Nanosheets with Exposed {001} Facets As an Effective Bifunctional Layer for Dye- Sensitized Solar Cells", 《ACS APPLIED MATERIALS INTERFACES》 * |
| 董业硕: "TiO2/纳米铁改性与晶面优化及氧化-还原特性调控的研究", 《中国优秀博硕士学位论文全文数据库(博士)工程科技Ⅰ辑》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111036210B (en) | 2022-09-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Pan et al. | Recent progress in 2D metal-organic framework photocatalysts: synthesis, photocatalytic mechanism and applications | |
| Li et al. | Anchoring single-unit-cell defect-rich bismuth molybdate layers on ultrathin carbon nitride nanosheet with boosted charge transfer for efficient photocatalytic ciprofloxacin degradation | |
| CN103143380B (en) | Solvent evaporation method for preparing graphite phase carbon nitride/{001} surface exposed anatase phase titanium dioxide nano composite material | |
| CN108671907B (en) | Platinum/titanium dioxide nanoflower composite material and preparation method and application thereof | |
| CN105688970B (en) | g‑C3N4The auto-dope Bi of modification2WO6Composite photo-catalyst and its preparation method and application | |
| WO2021212923A1 (en) | P-n heterojunction composite material supported on surface of nickel foam, preparation method therefor and use thereof | |
| CN109806876B (en) | Magnetic ZnFe2O4Graphene nano composite photocatalyst and preparation method and application thereof | |
| Zhang et al. | Iron phthalocyanine nanodots decorated ultra-thin porous carbon nitride: a combination of photocatalysis and Fenton reaction to achieve two-channel efficient tetracycline degradation | |
| CN110252352B (en) | Carbon quantum dot modified bismuth tungstate/ordered macroporous fluorine-doped tin oxide composite photocatalyst and preparation method and application thereof | |
| CN105195131A (en) | Preparation method of graphene quantum dot/vanadium-doped mesoporous titanium dioxide composite photocatalyst | |
| Zhang et al. | Facile preparation of high-performance hydrochar/TiO2 heterojunction visible light photocatalyst for treating Cr (VI)-polluted water | |
| Rasheed et al. | Highly efficient photocatalytic degradation of the Tetracycline hydrochloride on the α-Fe2O3@ CN composite under the visible light | |
| Zhang et al. | Construction of precious metal-loaded BiOI semiconductor materials with improved photocatalytic activity for microcystin-LR degradation | |
| Chen et al. | Synthesis of halloysite nanotubes supported Bi-modified BaSnO3 photocatalysts for the enhanced degradation of methylene blue under visible light | |
| CN111185210A (en) | Titanium carbide/titanium dioxide/black phosphorus nanosheet composite photocatalyst and preparation method and application thereof | |
| CN108579738B (en) | Gold nanoparticle/titanium dioxide nanoflower composite material and preparation method and application thereof | |
| CN110787795A (en) | Multilayer double-hole structure composite photocatalyst and preparation and application thereof | |
| CN111686767B (en) | Microspherical Bi3O4Preparation and application of Cl/BiOI compound | |
| CN111036210B (en) | (001) Surface exposed-three-dimensional laminated structure TiO 2 Preparation method of/nano-iron composite catalyst | |
| CN104858425B (en) | Method for weakening oxidization of metal nanoparticles | |
| Li et al. | Chemical etching and phase transformation of Nickel-Cobalt Prussian blue analogs for improved solar-driven water-splitting applications | |
| CN111359633B (en) | Z-type magnetic composite visible light catalyst and preparation and application thereof | |
| Shchukin et al. | Titanium and iron oxide-based magnetic photocatalysts for oxidation of organic compounds and sulfur dioxide | |
| CN112439403A (en) | Montmorillonite-titanium dioxide-graphene composite photocatalyst with pillared structure and preparation method thereof | |
| CN113941341A (en) | Tin disulfide compound for photocatalytic degradation of dye |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |