CN111715237B - Preparation method and application of magnetic nickel-palladium bimetallic supported titanium dioxide nano material - Google Patents
Preparation method and application of magnetic nickel-palladium bimetallic supported titanium dioxide nano material Download PDFInfo
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- CN111715237B CN111715237B CN202010585648.5A CN202010585648A CN111715237B CN 111715237 B CN111715237 B CN 111715237B CN 202010585648 A CN202010585648 A CN 202010585648A CN 111715237 B CN111715237 B CN 111715237B
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 63
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 52
- BSIDXUHWUKTRQL-UHFFFAOYSA-N nickel palladium Chemical compound [Ni].[Pd] BSIDXUHWUKTRQL-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 62
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 24
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 18
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 238000010531 catalytic reduction reaction Methods 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 238000005342 ion exchange Methods 0.000 claims abstract description 8
- 238000006722 reduction reaction Methods 0.000 claims abstract description 8
- 230000009467 reduction Effects 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 229910005581 NiC2 Inorganic materials 0.000 claims description 3
- 101150003085 Pdcl gene Proteins 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- 230000004044 response Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000007210 heterogeneous catalysis Methods 0.000 abstract description 2
- 238000005470 impregnation Methods 0.000 abstract description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 23
- 239000000243 solution Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 235000019253 formic acid Nutrition 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 11
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000007885 magnetic separation Methods 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 229910002666 PdCl2 Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical group Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000019254 sodium formate Nutrition 0.000 description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- B01J35/33—
-
- B01J35/394—
-
- B01J35/51—
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention relates to the technical field of heterogeneous catalysis, in particular to a preparation method and application of a magnetic nickel-palladium bimetallic supported titanium dioxide nano material. The preparation method comprises the following steps: preparing titanate; adding titanate into a nickel source for ion exchange, centrifuging, washing, drying, and calcining in a reducing atmosphere to obtain a magnetic nickel-loaded titanium dioxide material; adding the nickel-supported titanium dioxide material into a palladium source for impregnation reduction, and then centrifuging, washing and drying to obtain the magnetic nickel-palladium bimetallic supported titanium dioxide nano material. The preparation method has the advantages of simple process, high efficiency and easy scale production; the material prepared by the invention has the characteristics of spherical flower-shaped appearance, high magnetic response intensity, uniform attachment of simple substance palladium on the surface of nickel particles and high exposure; the material prepared by the invention shows excellent activity in a test of catalytic reduction of hexavalent chromium.
Description
Technical Field
The invention relates to the technical field of heterogeneous catalysis, in particular to a preparation method and application of a magnetic nickel-palladium bimetallic supported titanium dioxide nano material.
Background
In recent years, prevention and treatment of hexavalent chromium pollution are important issues for water resource environmental protection. Among the chromium pollution treatment methods, the catalytic reduction treatment method using formic acid (FA, HCOOH) as a reducing agent is most effective and has the characteristics of environmental protection. Among them, nano noble metal palladium (Pd) shows a very outstanding catalytic performance due to its excellent quantum size effect. However, the cost of the noble metal palladium is high, so how to efficiently utilize the palladium-based catalyst, rapidly separate and recycle the palladium-based catalyst is the key to efficiently treat hexavalent chromium pollution at low cost. The supported catalyst has high exposure degree and high utilization rate of active components, and is also an effective method for solving the problem of easy agglomeration of the palladium-based catalyst at present. In addition, the simple substance nickel has good magnetism, can introduce a catalyst to realize magnetic separation, and is favorable for separation and recovery. Therefore, combining nickel palladium and preparing a bimetallic supported catalyst at the same time is an effective method for solving the above problems. However, bimetallic materials are currently prepared by reduction using mixed precursor salts (which may involve large amounts of organic solvents), resulting in active site masking, which in turn impairs catalytic performance. The challenge remains how to rapidly prepare palladium-based nanomaterials which can be magnetically separated, have high exposure and high catalytic activity.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a magnetic nickel-palladium bimetallic supported titanium dioxide nano material with simple process and high efficiency, and also provides an application of the magnetic nickel-palladium bimetallic supported titanium dioxide nano material in catalyzing formic acid to reduce hexavalent chromium.
The invention provides a preparation method of a magnetic nickel-palladium bimetallic supported titanium dioxide nano material, which comprises the following steps:
s1, preparing titanate;
s2, adding titanate into a nickel source to perform an ion exchange reaction, centrifuging, washing, drying, and calcining and reducing in a reducing atmosphere to obtain a magnetic nickel-loaded titanium dioxide material;
s3, adding the nickel-supported titanium dioxide material obtained in the step S2 into a palladium source for dipping reduction, and then centrifuging, washing and drying to obtain the magnetic nickel-palladium bimetallic supported titanium dioxide nano material.
Further, in step S1, the preparation process of titanate is as follows: adding amorphous titanium dioxide into an alkali solution for hydrothermal reaction to obtain titanate.
Further, the alkali solution is ammonia, ethylenediamine, triethylamine or other organic amine solution.
Further, the temperature of the hydrothermal reaction was 150 ℃ and the time was 12 hours.
Further, in step S2, the nickel source is NiCl2·6H2O、NiC2O4·4H2O or Ni (NO)3)2·6H2Any of O, amorphous titanium dioxide and a nickel sourceThe mass ratio of the medium nickel ions is 1 (5-20).
Further, in step S2, the reaction temperature of the ion exchange reaction is 25 to 40 ℃, and the reaction time is 12 hours.
Further, in step S2, the rotation speed of the centrifuge is 3000 to 10000rpm during the centrifugation process, and the centrifugation time is 3 min; the drying temperature is 60 ℃, and the drying time is 12 h.
Further, in step S2, calcination is performed in H2The calcination is carried out in a reduction atmosphere of/Ar mixed gas, the calcination temperature is 500 ℃, the calcination time is 2h, and the temperature rise rate in the calcination process is 2.5 ℃/min.
Further, PdCl is selected as the palladium source2The mass ratio of the nickel-supported titanium dioxide material to the palladium source is 5: 1.
Further, the reaction temperature of the impregnation reduction reaction was 30 ℃ and the time was 10 hours.
Further, in step S3, the rotation speed of the centrifuge is 3000 to 10000rpm during the centrifugation process, and the centrifugation time is 3 min; the drying temperature is 60 ℃, and the drying time is 12 h.
The invention also provides the magnetic nickel-palladium bimetallic load titanium dioxide nano material prepared by the preparation method.
The magnetic nickel-palladium bimetallic supported titanium dioxide nano material prepared by the preparation method can be applied to catalytic reduction experiments, realizes high-efficiency catalytic reduction of hexavalent chromium under the condition of taking formic acid as a reducing agent, and shows excellent catalytic activity, convenient magnetic separation performance and good catalytic stability.
The method has the advantages of simple process, high efficiency and easy scale production; the whole nano material prepared by the method is in a spherical flower shape, nickel is embedded on a titanium dioxide carrier, and simple substance palladium is uniformly attached to the surface of nickel particles; the nano material prepared by the invention shows excellent activity in a hexavalent chromium catalytic reduction experiment.
The technical scheme provided by the invention has the beneficial effects that:
(1) the preparation method provided by the invention has the characteristics of simple process, high efficiency and easiness in scale production;
(2) the invention utilizes titanate and Ni2+Carrying out ion exchange, carrying out subsequent reduction treatment to obtain a supported material with uniformly distributed elemental metal, and simultaneously introducing magnetic elemental nickel to easily realize separation and recovery of the catalyst material;
(3) the magnetic nickel-palladium bimetallic load titanium dioxide nano material prepared by the preparation method provided by the invention has a spherical flower-like microscopic morphology, and shows monodispersity, good crystal form, high magnetic response strength, developed pore structure (10.0 nm) and large specific surface area (119.7 m)2The characteristics of/g) and the like;
(4) based on the advantages of physical property structure and bimetal, the magnetic nickel-palladium bimetal loaded titanium dioxide nano material prepared by the invention has excellent catalytic performance on formic acid, realizes high-efficiency catalytic reduction of hexavalent chromium, is easy to magnetically separate and recover, and has good cycle stability.
Drawings
Fig. 1 is a process flow chart of preparing a magnetic nickel-palladium bimetallic supported titanium dioxide nanomaterial according to embodiment 1 of the present invention.
Fig. 2 is a scanning electron microscope image of the magnetic nickel-palladium bimetallic supported titanium dioxide nanomaterial prepared in example 1 of the present invention.
Fig. 3 is a transmission electron microscope image of the magnetic nickel-palladium bimetallic supported titania nanomaterial prepared in example 1 of the present invention.
Fig. 4 is a graph representing the magnetic response strength of the magnetic nickel-palladium bimetallic supported titanium dioxide nanomaterial prepared in example 1 of the present invention.
Fig. 5 is a kinetic curve diagram of the magnetic nickel-palladium bimetallic supported titanium dioxide nanomaterial prepared in example 1 of the present invention for catalytic reduction of hexavalent chromium.
Fig. 6 is a diagram showing the cycle effect of the magnetic nickel-palladium bimetallic supported titanium dioxide nanomaterial prepared in example 1 of the present invention in catalytic reduction of hexavalent chromium.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be further described with reference to the accompanying drawings and examples.
Example 1:
weighing 0.6g of amorphous titanium dioxide, dispersing the amorphous titanium dioxide in 90mL of 1.3mol/L ethylenediamine solution, uniformly stirring, transferring the solution into a polytetrafluoroethylene high-pressure reaction kettle, and reacting at 150 ℃ for 12 hours to obtain titanate; adding 600mL of 10g/L Ni into the prepared titanate2+(Ni2+Derived from NiCl2·6H2O) in water solution, ion-exchanging at 30 deg.C for 12H, centrifuging at 8000rpm for 3min, washing with deionized water, drying at 60 deg.C for 12H, placing in muffle furnace, and drying in H2Calcining for 2 hours at 500 ℃ in a reduction atmosphere of/Ar mixed gas, and setting the temperature rise rate of a muffle furnace to be 2.5 ℃/min to obtain a magnetic nickel-loaded titanium dioxide material; 0.15g of nickel-loaded titanium dioxide material is weighed and added into 5mL of PdCl with the concentration of 6g/L2Soaking and reducing the solution in 30 ℃ constant temperature water bath for 10h, centrifuging at 8000rpm for 3min, washing with deionized water, and vacuum drying at 60 ℃ for 12h to obtain the magnetic nickel-palladium bimetallic supported titanium dioxide nano material (Pd-Ni/fTiO)2And f represents a flower shape).
The process flow diagram of the above preparation process is shown in figure 1.
Scanning electron microscope characterization is carried out on the magnetic nickel-palladium bimetallic supported titanium dioxide nano material prepared in the example 1, and as shown in figure 2, the material shows a monodisperse spherical flower-shaped morphology with a specific surface area of 119.7m2(g), the pore channel is 10.0nm, and no other impurity phase is seen.
Transmission electron microscope analysis is performed on the magnetic nickel-palladium bimetallic supported titanium dioxide nanomaterial prepared in example 1, and as shown in fig. 3, nickel-palladium nanoparticles with smaller particles are uniformly distributed on the surface of a nanosheet of titanium dioxide (fig. 3 a). The result of the high-power transmission electron microscope shows that the lattice spacing is 0.230nm and is consistent with the (111) crystal face spacing of palladium, and the lattice spacing is 0.240nm and is consistent with the lattice fringes of the Ni (110) crystal face, so that the palladium nano-particles are successfully deposited on the surface of the nickel particles by using a metal replacement deposition method (fig. 3 b).
Magnetic response strength analysis was performed on the magnetic nickel-palladium bimetallic supported titanium dioxide nanomaterial prepared in example 1, as shown in fig. 4, it can be found from fig. 4 that the saturation magnetic strength was 3.13emu/g, and there was no remanence and coercivity in the curve, indicating the superparamagnetism of the magnetic nickel-palladium bimetallic supported titanium dioxide nanomaterial. As can be seen from the inset in the lower right corner of FIG. 4, the magnetic nickel-palladium bimetallic supported titanium dioxide nanomaterial can be well dispersed in a solvent, and can also be separated from a reaction system by the attraction of a magnet, thereby proving the good dispersibility and the rapid magnetic responsiveness of the material in the solution.
The magnetic nickel-palladium bimetallic supported titanium dioxide nano material prepared in the example 1 is applied to a hexavalent chromium catalytic reduction experiment (the experimental condition is that the total volume is 10mL of aqueous solution, and the aqueous solution contains 0.45mol L–1Mixed solution of HCOOH and HCOONa and 2mmol L–1K of2Cr2O7The addition amount of the catalyst nano material is 3mg, the experimental temperature is 25 ℃), and the obtained kinetic curve graph is shown in fig. 5, and as can be seen from fig. 5, when Formic Acid (FA) is used alone, the concentration of hexavalent chromium is almost unchanged, and the efficiency is very low when a reducing agent is used alone; when the catalyst nano material is used alone, the weak adsorption effect is caused due to the large specific surface area of the nano material; when the magnetic nickel-palladium bimetallic load titanium dioxide nano material (Pd-Ni/fTiO)2) When the nano-titanium dioxide exists with formic acid, the concentration of hexavalent chromium is rapidly reduced, which is caused by the titanium dioxide nano-material Pd-Ni/fTiO2Good catalytic performance on formic acid is realized, so that hexavalent chromium is reduced quickly; when the catalyst nano material is nickel-loaded titanium dioxide nano material (Ni/fTiO)2) The concentration of hexavalent chromium is not obviously changed, and the active component of the catalyst is proved to be metal palladium, and the main function of the metal nickel is to perform magnetic separation and recovery.
Referring to fig. 6, which is a result of a cycle experiment of the magnetic nickel-palladium bimetallic supported titanium dioxide nanomaterial prepared in example 1 for catalyzing formic acid to reduce hexavalent chromium, it can be seen from fig. 6 that the material prepared in example 1 not only shows excellent catalytic activity, but also has very good cycle stabilityAfter the material is continuously recycled for 10 times, the catalytic efficiency is not obviously reduced; wherein, the operation process of the circulation experiment is as follows: after the primary catalytic reduction reaction is finished, separating and collecting the nano material by utilizing the magnet adsorption, fully washing the nano material by using deionized water, drying the washed nano material, and then adding the collected nano material into the newly configured K2Cr2O7Adding HCOOH/HCOONa mixed solution, carrying out the next catalytic reduction experiment, and repeating the operations in sequence.
Example 2:
weighing 0.6g of amorphous titanium dioxide, dispersing the amorphous titanium dioxide in 90mL of 1.3mol/L ammonia water solution, uniformly stirring, transferring the amorphous titanium dioxide into a polytetrafluoroethylene high-pressure reaction kettle, and reacting for 12 hours at 150 ℃ to obtain titanate; adding 600mL of 20g/L Ni into the prepared titanate2+(Ni2+Derived from NiC2O4·4H2O) in water solution, performing ion exchange at 30 ℃ for 12H, centrifuging at 6000rpm for 3min, washing with deionized water, drying at 60 ℃ for 12H, placing in a muffle furnace, and performing H2Calcining for 2 hours at 500 ℃ in an/Ar mixed gas reducing atmosphere, and setting the heating rate of a muffle furnace to be 2.5 ℃/min to obtain a magnetic nickel-loaded titanium dioxide material; 0.10g of nickel-loaded titanium dioxide material was weighed into 5mL of 4g/L PdCl2Soaking and reducing the solution in 30 ℃ constant-temperature water bath for 10h, centrifuging the solution for 3min at the rotating speed of 5000rpm, washing the solution with deionized water, and drying the solution in vacuum at 60 ℃ for 12h to obtain the magnetic nickel-palladium bimetallic load titanium dioxide nano material (Pd-Ni/fTiO)2)。
Example 3:
weighing 0.5g of amorphous titanium dioxide, dispersing the amorphous titanium dioxide in 90mL of 1.3mol/L triethylamine solution, uniformly stirring, transferring the amorphous titanium dioxide into a polytetrafluoroethylene high-pressure reaction kettle, and reacting for 12 hours at 150 ℃ to obtain titanate; the prepared titanate is added into 600mL of Ni with the concentration of 5g/L2+(Ni2+Derived from Ni (NO)3)2·6H2O) in water solution, ion-exchanging at 30 deg.C for 12H, centrifuging at 8000rpm for 3min, washing with deionized water, drying at 60 deg.C for 12H, placing in muffle furnace, and drying in H2Calcining for 2 hours at 500 ℃ in an/Ar mixed gas reducing atmosphere, and setting the heating rate of a muffle furnace to be 2.5 ℃/min to obtain a magnetic nickel-loaded titanium dioxide material; 0.20g of nickel-loaded titanium dioxide material was weighed into 5mL of 8g/L PdCl2Soaking and reducing the solution in 30 ℃ constant-temperature water bath for 10h, centrifuging at 6000rpm for 3min, washing with deionized water, and vacuum drying at 60 ℃ for 12h to obtain the magnetic nickel-palladium bimetallic supported titanium dioxide nano material (Pd-Ni/fTiO)2)。
The features of the embodiments and embodiments described herein above may be combined with each other without conflict.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. A preparation method of a magnetic nickel-palladium bimetallic supported titanium dioxide nano material is characterized by comprising the following steps:
s1, adding amorphous titanium dioxide into an alkali solution for hydrothermal reaction to obtain titanate; the alkali solution is any one of ammonia water, ethylenediamine or triethylamine;
s2, adding titanate into a nickel source to perform an ion exchange reaction, centrifuging, washing, drying, and calcining in a reducing atmosphere to obtain a magnetic nickel-loaded titanium dioxide material; the mass ratio of the amorphous titanium dioxide to the nickel ions in the nickel source is 1 (5-20);
s3, adding the nickel-supported titanium dioxide material obtained in the step S2 into a palladium source for dipping reduction, and then centrifuging, washing and drying to obtain a magnetic nickel-palladium bimetallic supported titanium dioxide nano material; wherein the mass ratio of the nickel-loaded titanium dioxide material to the palladium source is 5: 1.
2. The method for preparing the magnetic Ni-Pd bimetallic supported TiO 2 nanomaterial of claim 1, wherein in step S2, NiCl is used as the Ni source2·6H2O、NiC2O4·4H2O or Ni (NO)3)2·6H2Any one of O.
3. The method for preparing the magnetic Ni-Pd bimetallic supported titania nano-material as claimed in claim 1, wherein in step S2, the material is calcined in H2The reaction is carried out in an atmosphere of/Ar mixed gas.
4. The method for preparing the magnetic Ni-Pd bimetallic supported titania nanomaterial of claim 1, wherein in step S3, PdCl is used as the palladium source2。
5. The method for preparing the magnetic nickel-palladium bimetallic supported titanium dioxide nanomaterial according to claim 1, wherein in step S3, the rotation speed of a centrifuge in the centrifugation process is 3000-10000 rpm, and the centrifugation time is 3 min; the drying temperature is 60 ℃, and the drying time is 12 h.
6. A magnetic nickel-palladium bimetallic supported titanium dioxide nano material is characterized by being prepared by the preparation method of any one of claims 1-5.
7. Use of the magnetic nickel-palladium bimetallic supported titania nanomaterial prepared by the preparation method of any one of claims 1-5, wherein the magnetic nickel-palladium bimetallic supported titania nanomaterial is used for catalytic reduction of hexavalent chromium.
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