CN108906059B - TiO 22Magnetic porous composite material and preparation method thereof - Google Patents
TiO 22Magnetic porous composite material and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims description 12
- 238000007747 plating Methods 0.000 claims abstract description 95
- 238000003756 stirring Methods 0.000 claims abstract description 60
- 239000000126 substance Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 25
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 17
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 174
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 132
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 71
- 230000003213 activating effect Effects 0.000 claims description 61
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 239000001913 cellulose Substances 0.000 claims description 36
- 229920002678 cellulose Polymers 0.000 claims description 36
- 238000001914 filtration Methods 0.000 claims description 34
- 229910052759 nickel Inorganic materials 0.000 claims description 33
- 230000004913 activation Effects 0.000 claims description 32
- 239000011259 mixed solution Substances 0.000 claims description 29
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 24
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 23
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 239000012279 sodium borohydride Substances 0.000 claims description 17
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 17
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 15
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 14
- 239000001509 sodium citrate Substances 0.000 claims description 14
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 14
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000019013 Viburnum opulus Nutrition 0.000 claims description 8
- 244000071378 Viburnum opulus Species 0.000 claims description 8
- 239000012670 alkaline solution Substances 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 238000005096 rolling process Methods 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 238000003892 spreading Methods 0.000 claims description 6
- 230000007480 spreading Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000009775 high-speed stirring Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 2
- 238000013329 compounding Methods 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 230000004907 flux Effects 0.000 abstract description 4
- 230000003287 optical effect Effects 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 4
- 210000002421 cell wall Anatomy 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 238000003980 solgel method Methods 0.000 abstract description 2
- 239000011521 glass Substances 0.000 description 40
- 239000012153 distilled water Substances 0.000 description 35
- 230000001699 photocatalysis Effects 0.000 description 7
- 238000013459 approach Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 238000011010 flushing procedure Methods 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000002023 wood Substances 0.000 description 5
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 231100000378 teratogenic Toxicity 0.000 description 1
- 230000003390 teratogenic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B01J35/23—
-
- B01J35/33—
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
Abstract
The invention relates to a nano structure, in particular to TiO2The composite material takes nano lignocellulose as a skeleton, firstly, the cell wall of the lignocellulose is stripped, and a large number of pore structures appear on the surface of the lignocellulose, so that the porous nano lignocellulose is prepared; then carrying out chemical Ni plating on the surface for 1 time and 2 times, adding nano graphene in the chemical Ni plating process for 2 times, and coating a metal layer on the surface of the porous nano lignocellulose to form a magnetic cylindrical structure; compounding the cylindrical structure, TBOT and nano-graphene by a sol-gel method, continuously stirring and uniformly compounding in the compounding process, calcining the composite structure at high temperature, so that the composite coating coated on the surface pore structure can collapse, and finally, the cylindrical structure and the nano-TiO are compounded2Realizes uniform composition with nano-graphene, successfully prepares Ni-NiO/GO-TiO2A magnetic porous cylindrical structure. The invention can capture the luminous flux and the longest optical path to the maximum extent.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to TiO2A magnetic porous composite material and a preparation method thereof.
Background
With the acceleration of the national industrialization process, toxic and harmful industrial wastewater is continuously generated in the production process of enterprises. The general industrial wastewater can adopt a conventional industrial sewage treatment process, mainly adopts biochemical treatment, and is discharged into a storage water body after reaching the standard; can also be directly discharged into a sewage treatment plant in an industrial park through simple pretreatment. Some of the heavy metal ions in them are carcinogenic, teratogenic and teratogenicThe effect of mutation poses a great threat to human health. The search for pollution-free, recyclable photocatalytic materials to ameliorate the growing environmental pollution has been pressing. The nano titanium dioxide-based photocatalytic material can reduce heavy metal ions in a solution into nontoxic metals so as to respectively recycle the metals and the catalytic material, has the potential of directly utilizing solar energy, and shows wide application prospect in the aspect of wastewater treatment. At present, the adopted nano titanium dioxide based photocatalytic material is due to nano TiO2Is easily affected by the loss of active components, and is difficult to recycle and reuse; secondly, the shape and size of the hollow catalytic material are difficult to control, the operation procedure is complex, and the photocatalytic activity is low; moreover, the solar energy utilization rate is low, and the electron and hole recombination efficiency of the photocatalytic material is higher. The method for reducing heavy metal ions by utilizing the nano titanium dioxide-based magnetic porous photocatalytic material which is easy to recycle and can be recycled is the most preferable method, and the research and development of the nano titanium dioxide-based magnetic porous photocatalytic material for reducing the heavy metal ions also becomes one of effective ways for realizing the practicability of recycling the heavy metal ions and reducing the cost.
Disclosure of Invention
The invention aims to overcome the defects and provide TiO2A magnetic porous composite material and a preparation method thereof.
The technical scheme of the invention is as follows: TiO 22The magnetic porous composite material takes nano lignocellulose as a framework and has porous Ni-NiO/GO-TiO surface2The composite cylindrical structure can capture the luminous flux and the longest optical path to the maximum extent.
The invention also provides TiO2The preparation method of the basic magnetic porous composite material comprises the following steps:
step 1, weighing lignocellulose, dissolving the lignocellulose in deionized water, and uniformly stirring the lignocellulose until uniform suspension is formed;
step 2, dispersing lignocellulose by using an ultrasonic signal generator; the dispersion time is 180 minutes, the power is 960W, the ultrasonic water bath temperature is 30-40 ℃, and the climate environment influences the temperature setting.
Step 3, preparing an activating solution A solution, an activating solution B solution and a chemical plating solution C solution, wherein the activating solution A solution is a mixed solution of concentrated hydrochloric acid and nickel sulfate, and the concentration of the mixed solution is 0.7-0.9 mL/g; the activating solution B is a mixed solution of sodium hydroxide and sodium borohydride, and the mass ratio of the activating solution B to the sodium borohydride is 0.7-0.9: 0.9-1.1; and the solution C is a mixed plating solution of nickel sulfate, sodium citrate, sodium hypophosphite and thiourea, and the mass ratio of the plating solution C is nickel sulfate: sodium citrate: sodium hypophosphite: thiourea 8.5-12: 8-10: 7-10: 0.01-0.03;
step 4, the micro/nano lignocellulose prepared in the step 2 is used as a sample, the sample is put into an activating solution A for activation, the sample is taken out after filtration and is put into an activating solution B for activation, the sample is taken out after successful activation, the sample is put into a chemical plating solution C for nickel plating, then the chemical plating solution is reconfigured and chemical nickel plating is continuously carried out, 2 times of nickel plating treatment are carried out, filtration is carried out for 2 times, the sample is dried, the dried sample is filtered for 2 times, metallized cellulose with uniform appearance and appearance is obtained, and the sample is stored;
and 5, taking the metallized cellulose prepared in the step 4 as a precursor, and weighing 0.1-0.15g of metallized cellulose to disperse into ethanol: TBOT (tetrabutyl titanate) is mixed with ethanol and TBOT solution in a ratio of 45-55:0.5-1.5, the mixture is stirred uniformly and then placed in a water bath to ensure that the ethanol is volatilized completely, the mixed solution is converted into a cracked white flaky material and is paved on the bottom of the whole container, and finally the dried powder is placed in a muffle furnace to be calcined to obtain Ni-NiO/GO-TiO2Magnetic porous cylindrical composite material.
Further, in the step 1, an electronic balance is used for weighing, the model of the ultrasonic signal generator is SM-1200D, in the step 2, an amplitude transformer of the ultrasonic signal generator is placed at a position which is half of the height of the solution, the amplitude transformer is positioned at the center of the circle of the solution, and the amplitude transformer is far away from a temperature control sensor of the ultrasonic signal generator.
Further, the concentration of the activating solution A is 0.8mL/g, the mass ratio of sodium hydroxide to sodium borohydride in the activating solution B is 0.8:1, and the mass ratio of nickel sulfate, sodium citrate, sodium hypophosphite to thiourea in the solution C is 9.9: 9: 8.4: 20; in step 5, 0.1g of metallized cellulose is weighed, and the weight ratio of ethanol: TBOT (tetrabutyl titanate) ═ 50: 1.
Further, in step 2, in the ultrasonic water bath process, the container in which the lignocellulose is dissolved is placed in the device for placing ice cubes, the ice cubes are continuously replaced in the process, and the frequency of replacing the ice cubes is as follows: changing every 15 minutes in summer and every 30 minutes in winter; the temperature of the ultrasonic water bath is about 35 ℃.
Further, in step 4, the micro/nano lignocellulose prepared in step 2 is used as a sample, the sample is put into an activating solution A for activation for 15 minutes and is uniformly stirred, the sample is stirred for 1 time every 2 minutes and is filtered for 2 times by a double-layer filter screen, the sample is taken out and is put into an activating solution B for activation until no liquid drips, the activation time is 90 seconds, the sample is uniformly stirred and is stirred for 1 time every 30 seconds, the sample is filtered for 2 times by the double-layer filter screen, the sample is filtered by a back-and-forth snowball rolling mode, the sample is taken out after the activation is successful, when no activating solution drips on the surface, the sample is put into a chemical plating solution C, the pH value is 9-9.5, the nickel is plated for 25-35 minutes under the condition of 60 ℃, the specific chemical plating time is according to the laboratory conditions, the chemical plating solution is reconfigured and the nickel is continuously plated, the sample is filtered for 2 times by the double-layer filter screen after, drying the sample, filtering the dried sample for 2 times by adopting a double-layer filter screen, uniformly shaking the filter screen to obtain the metallized cellulose with uniform appearance and appearance, and preserving the sample.
Further, in step 4, the successful activation is marked by the following phenomena: and if the sample does not have the mark phenomenon of successful activation, the sample is immediately reactivated until the mark phenomenon of successful activation appears.
Further, in step 5, under high-speed stirring, mixing the metal cellulose, ethanol and TBOT (tetrabutyl titanate), stirring for 25-30 minutes, shaking the container once every 2-5 minutes, and then placing the uniformly stirred mixed solution into a water bath with the water temperature of 95 ℃ for reaction to obtain the white flaky material.
Further, in the step 5, the muffle furnace is FSX2-12-15N, the calcination is carried out for 6 hours at the temperature of 600 ℃, and the muffle furnace is arrangedPreheating for 30min at 600 ℃, heating for 6 hours at 600 ℃, and keeping the temperature at 600 ℃ for 2 hours in 3 time periods to finally obtain Ni-NiO/GO-TiO2Magnetic porous cylindrical composite material.
Further, in the step 3, the pH value of the solution C is 9-9.5; measuring pH value with acidity meter before adjusting pH value, wherein the normal range is 5.2-5.8, and if pH value is not within 5.2-5.8, reconfiguring plating solution or calibrating acidity meter; the method comprises the steps of calibrating an acidity meter by using deionized water, calibrating by using an alkaline solution with the pH value of 9.15, washing the acidity meter by using clear water after the calibration is finished, readjusting the pH value of the solution to be within a normal range, adjusting the pH value of the plating solution to be 9-9.5 by using ammonia water, determining the final pH value of the plating solution according to the initially configured pH value of the plating solution, and adjusting the pH value of the plating solution to be within a range of 9-9.5.
The invention has the beneficial effects that:
1. the nanometer lignocellulose is used as the framework, the framework automatically disappears in the technical process of preparing the magnetic porous cylindrical structure, and the conventional demolding technical process is omitted;
2. by adopting 2 times of chemical plating of Ni, the compounding time of the cylindrical structure, TBOT and nano graphene is reasonably adjusted, and the controllable magnetic porous cylindrical structure can capture the luminous flux and the longest optical path to the maximum extent.
3、Ni-NiO/GO-TiO2The adjustment and control of the NiO/Ti ratio in the magnetic porous cylindrical structure does not need to add O-related materials, and the ideal NiO/Ti ratio can be obtained only by reasonably adjusting and controlling the oxidation time in the heat treatment process of the composite structure.
4. In the chemical nickel plating process of the surface of the lignocellulose for multiple times, whether the activation is successful or not is judged by adopting the phenomena of color change of the surface of the sample and air bubbles released between gaps of the sample, so that the method is more visual and rapid.
Drawings
FIG. 1 is a schematic view of a process for preparing a composite material according to the present invention;
fig. 2 is a schematic diagram of light reflection of a cylindrical structure.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various modifications and changes may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents may fall within the scope of the invention as defined in the claims appended hereto.
TiO 22The magnetic porous composite material takes nano lignocellulose as a framework and has porous Ni-NiO/GO-TiO surface2The composite cylindrical structure can capture the luminous flux and the longest optical path to the maximum extent.
TiO 22The preparation method of the basic magnetic porous composite material comprises the following steps:
step 1, weighing lignocellulose, dissolving the lignocellulose in deionized water, and uniformly stirring the lignocellulose until uniform suspension is formed;
step 2, dispersing lignocellulose by using an ultrasonic signal generator; the dispersion time is 180 minutes, the power is 960W, the ultrasonic water bath temperature is 30-40 ℃, and the climate environment influences the temperature setting.
Step 3, preparing an activating solution A solution, an activating solution B solution and a chemical plating solution C solution, wherein the activating solution A solution is a mixed solution of concentrated hydrochloric acid and nickel sulfate, and the concentration of the mixed solution is 0.7-0.9 mL/g; the activating solution B is a mixed solution of sodium hydroxide and sodium borohydride, and the mass ratio of the activating solution B to the sodium borohydride is 0.7-0.9: 0.9-1.1; and the solution C is a mixed plating solution of nickel sulfate, sodium citrate, sodium hypophosphite and thiourea, and the mass ratio of the plating solution C is nickel sulfate: sodium citrate: sodium hypophosphite: thiourea 8.5-12: 8-10: 7-10: 0.01-0.03;
step 4, the micro/nano lignocellulose prepared in the step 2 is used as a sample, the sample is put into an activating solution A for activation, the sample is taken out after filtration and is put into an activating solution B for activation, the sample is taken out after successful activation, the sample is put into a chemical plating solution C for nickel plating, then the chemical plating solution is reconfigured and chemical nickel plating is continuously carried out, 2 times of nickel plating treatment are carried out, filtration is carried out for 2 times, the sample is dried, the dried sample is filtered for 2 times, metallized cellulose with uniform appearance and appearance is obtained, and the sample is stored;
and 5, taking the metallized cellulose prepared in the step 4 as a precursor, and weighing 0.1-0.15g of metallized cellulose to disperse into ethanol:TBOT (tetrabutyl titanate) is mixed with ethanol and TBOT solution in a ratio of 45-55:0.5-1.5, the mixture is stirred uniformly and then placed in a water bath to ensure that the ethanol is volatilized completely, the mixed solution is converted into a cracked white flaky material and is paved on the bottom of the whole container, and finally the dried powder is placed in a muffle furnace to be calcined to obtain Ni-NiO/GO-TiO2Magnetic porous cylindrical composite material.
Further, in the step 1, an electronic balance is used for weighing, the model of the ultrasonic signal generator is SM-1200D, in the step 2, an amplitude transformer of the ultrasonic signal generator is placed at a position which is half of the height of the solution, the amplitude transformer is positioned at the center of the circle of the solution, and the amplitude transformer is far away from a temperature control sensor of the ultrasonic signal generator.
Further, the concentration of the activating solution A is 0.8mL/g, the mass ratio of sodium hydroxide to sodium borohydride in the activating solution B is 0.8:1, and the mass ratio of nickel sulfate, sodium citrate, sodium hypophosphite to thiourea in the solution C is 9.9: 9: 8.4: 20; in step 5, 0.1g of metallized cellulose is weighed, and the weight ratio of ethanol: TBOT (tetrabutyl titanate) ═ 50: 1.
Further, in step 2, in the ultrasonic water bath process, the container in which the lignocellulose is dissolved is placed in the device for placing ice cubes, the ice cubes are continuously replaced in the process, and the frequency of replacing the ice cubes is as follows: changing every 15 minutes in summer and every 30 minutes in winter; the temperature of the ultrasonic water bath is about 35 ℃.
Further, in step 4, the micro/nano lignocellulose prepared in step 2 is used as a sample, the sample is put into an activating solution A for activation for 15 minutes and is uniformly stirred, the sample is stirred for 1 time every 2 minutes and is filtered for 2 times by a double-layer filter screen, the sample is taken out and is put into an activating solution B for activation until no liquid drips, the activation time is 90 seconds, the sample is uniformly stirred and is stirred for 1 time every 30 seconds, the sample is filtered for 2 times by the double-layer filter screen, the sample is filtered by a back-and-forth snowball rolling mode, the sample is taken out after the activation is successful, when no activating solution drips on the surface, the sample is put into a chemical plating solution C, the pH value is 9-9.5, the nickel is plated for 25-35 minutes under the condition of 60 ℃, the specific chemical plating time is according to the laboratory conditions, the chemical plating solution is reconfigured and the nickel is continuously plated, the sample is filtered for 2 times by the double-layer filter screen after, drying the sample, filtering the dried sample for 2 times by adopting a double-layer filter screen, uniformly shaking the filter screen to obtain the metallized cellulose with uniform appearance and appearance, and preserving the sample.
Further, in step 4, the successful activation is marked by the following phenomena: and if the sample does not have the mark phenomenon of successful activation, the sample is immediately reactivated until the mark phenomenon of successful activation appears.
Further, in step 5, under high-speed stirring, mixing the metal cellulose, ethanol and TBOT (tetrabutyl titanate), stirring for 25-30 minutes, shaking the container once every 2-5 minutes, and then placing the uniformly stirred mixed solution into a water bath with the water temperature of 95 ℃ for reaction to obtain the white flaky material.
Further, in the step 5, the muffle furnace is FSX2-12-15N in model number, the calcining is carried out for 6 hours at the temperature of 600 ℃, the muffle furnace is set for 3 time periods, the preheating is carried out for 30min at the temperature of 600 ℃, the heating is carried out for 6 hours at the temperature of 600 ℃, the heat preservation is carried out for 2 hours at the temperature of 600 ℃, and finally the Ni-NiO/GO-TiO is obtained2Magnetic porous cylindrical composite material.
Further, in the step 3, the pH value of the solution C is 9-9.5; measuring pH value with acidity meter before adjusting pH value, wherein the normal range is 5.2-5.8, and if pH value is not within 5.2-5.8, reconfiguring plating solution or calibrating acidity meter; the method comprises the steps of calibrating an acidity meter by using deionized water, calibrating by using an alkaline solution with the pH value of 9.15, washing the acidity meter by using clear water after the calibration is finished, readjusting the pH value of the solution to be within a normal range, adjusting the pH value of the plating solution to be 9-9.5 by using ammonia water, determining the final pH value of the plating solution according to the initially configured pH value of the plating solution, and adjusting the pH value of the plating solution to be within a range of 9-9.5.
Example 1: TiO 22The preparation method of the basic magnetic porous composite material is shown in figure 1, and comprises the following specific steps:
(1) 0.6g of lignocellulose is weighed by an electronic balance, 300mL of distilled water is measured by a 500mL beaker, the weighed lignocellulose is dissolved in the distilled water, and the mixture is uniformly stirred by a glass rod until the beaker forms a uniform suspension.
(2) The SM-1200D ultrasonic signal generator is used for dispersing lignocellulose, and three points need to be paid attention to the adjustment of the amplitude transformer: 1. the amplitude transformer is placed at a half position of the height of the solution, 2, the amplitude transformer is positioned at the center of the circle of the solution, and 3, the amplitude transformer does not approach the temperature control sensor; the dispersion time is 180 minutes, the power is 960W, the beaker with the lignocellulose dissolved is placed in a device for placing ice blocks, the ice blocks are continuously replaced in the period, the frequency of replacing the ice blocks is different according to seasons, the ice is replaced every 15 minutes in summer, the ice is replaced every 30 minutes in winter, and the temperature of the ultrasonic water bath is always kept at about 35 ℃.
(3) Three 500mL beakers were taken, 200mL of distilled water in the first beaker and labeled a, 200mL of distilled water in the second beaker and labeled B, and 310mL of distilled water in the third beaker and labeled C. 2.4mL of concentrated hydrochloric acid was slowly poured into A, and after stirring well with a glass rod, 3g of nickel sulfate was added and stirred well. 2.4g of sodium hydroxide is slowly poured into the beaker B, and after being uniformly stirred by a glass rod, 3g of sodium borohydride is added and uniformly stirred. Placing a glass C filled with 310mL of distilled water in a constant-temperature water bath kettle at 60 ℃ for preheating for 15 minutes, taking the actual solution ratio according to 310mL of distilled water as a standard, evaporating part of water mainly due to preheating, and measuring 9.9g of nickel sulfate, 9.0g of sodium citrate, 8.4g of sodium hypophosphite and 20mg of thiourea in sequence and stirring and dissolving uniformly in sequence if the solution concentration is not deviated. Carefully observing the pH value of the acidimeter before adjusting the pH value, wherein the normal range is between 5.2 and 5.8, if the pH value is not between 5.2 and 5.8, reconfiguring the plating solution or calibrating the acidimeter, calibrating the acidimeter by adopting 2 ways, firstly calibrating the acidimeter by using deionized water, then calibrating the acidimeter by using an alkaline solution with the pH value of 9.15, flushing the acidimeter by using clean water after the calibration is finished, readjusting the pH value of the solution until the pH value is in the normal range, then adjusting the pH value of the plating solution to be between 9 and 9.5 by using ammonia water, and determining the pH value according to the initial pH value of the solution.
(4) Putting micro/nano lignocellulose prepared by ultrasonic as a sample into an activating solution A for activating for 15 minutes, uniformly stirring by using a glass rod, stirring 1 time by using the glass rod every 2 minutes, filtering 2 times by using a double-layer filter screen, taking out the sample, putting the sample into an activating solution B for activating till no liquid drips, wherein the activating time is 90 seconds, uniformly stirring by using the glass rod, stirring 1 time by using the glass rod every 30 seconds, filtering 2 times by using the double-layer filter screen, filtering the sample by adopting a back-and-forth snowball rolling mode, at the moment, the surface of the sample becomes black, releasing air bubbles between gaps, immediately reactivating the sample if the surface of the sample does not become black, releasing the air bubbles between the gaps, till the phenomenon is normal, then taking out till no activating solution drips on the surface, putting the sample into a chemical plating solution, keeping the pH value at 9-9.5, and plating nickel for 30 minutes at the temperature of 60 ℃, and after 30 minutes, reconfiguring the plating solution and continuously carrying out chemical nickel plating, after carrying out nickel plating treatment for 2 times, filtering for 2 times by adopting a double-layer filter screen, placing the sample on the surface of a dry wood chip with the length and the width of 8cm and the x of 3cm for drying treatment, filtering the dried sample for 2 times by adopting the double-layer filter screen, uniformly shaking the filter screen to obtain the metallized cellulose with uniform appearance and appearance, and storing the sample.
(5) Taking prepared metallized cellulose as a precursor, stirring at high speed by an electric stirrer, weighing 0.12g of metallized cellulose, dispersing the metallized cellulose into a mixed solution of 50mL of ethanol and 1mL of tetrabutyl titanate in a conical flask, stirring for 30 minutes, shaking the conical flask every 3 minutes, placing the uniformly stirred mixed solution in a water bath kettle with the water temperature of 95 ℃ to completely volatilize ethanol, converting the mixed solution into a cracked white flaky material and spreading the cracked white flaky material on the bottom of the whole conical flask, finally placing the dried powder in an FSX2-12-15N type muffle furnace for calcining at 600 ℃ for 6 hours, setting the muffle furnace for 3 time periods, preheating at 600 ℃ for 30min, heating at 600 ℃ for 6 hours, preserving the heat at 600 ℃ for 2 hours to obtain Ni-GO/NiO/TiO-TiO2A magnetic porous cylindrical structure.
Example 2: TiO 22The preparation method of the basic magnetic porous composite material comprises the following specific steps:
(1) 0.6g of lignocellulose is weighed by an electronic balance, 300mL of distilled water is measured by a 500mL beaker, the weighed lignocellulose is dissolved in the distilled water, and the mixture is uniformly stirred by a glass rod until the beaker forms a uniform suspension.
(2) The SM-1200D ultrasonic signal generator is used for dispersing lignocellulose, and three points need to be paid attention to the adjustment of the amplitude transformer: 1. the amplitude transformer is placed at a half position of the height of the solution, 2, the amplitude transformer is positioned at the center of the circle of the solution, and 3, the amplitude transformer does not approach the temperature control sensor; the dispersion time is 180 minutes, the power is 960W, the beaker with the lignocellulose dissolved is placed in a device for placing ice blocks, the ice blocks are continuously replaced in the period, the frequency of replacing the ice blocks is different according to seasons, the ice is replaced every 15 minutes in summer, the ice is replaced every 30 minutes in winter, and the temperature of the ultrasonic water bath is always kept at about 30 ℃.
(3) Three 500mL beakers were taken, 200mL of distilled water in the first beaker and labeled a, 200mL of distilled water in the second beaker and labeled B, and 310mL of distilled water in the third beaker and labeled C. Slowly pouring concentrated hydrochloric acid into the solution A, uniformly stirring the solution by using a glass rod, adding nickel sulfate, and uniformly stirring the solution to obtain a solution with the concentration of 0.7 mL/g. And slowly pouring sodium hydroxide into the beaker B, uniformly stirring by using a glass rod, adding sodium borohydride, and uniformly stirring, wherein the mass ratio of the sodium hydroxide to the sodium borohydride is 0.7: 0.9. Placing a glass C filled with 310mL of distilled water in a constant-temperature water bath kettle at 60 ℃ for preheating for 15 minutes, taking the actual solution ratio according to 310mL of distilled water as a standard, evaporating part of water mainly due to preheating, and measuring 8.5g of nickel sulfate, 8g of sodium citrate, 7g of sodium hypophosphite and 10mg of thiourea in sequence and stirring and dissolving uniformly in sequence if the solution concentration is not deviated. Carefully observing the pH value of the acidimeter before adjusting the pH value, wherein the normal range is between 5.2 and 5.8, if the pH value is not between 5.2 and 5.8, reconfiguring the plating solution or calibrating the acidimeter, calibrating the acidimeter by adopting 2 ways, firstly calibrating the acidimeter by using deionized water, then calibrating the acidimeter by using an alkaline solution with the pH value of 9.15, flushing the acidimeter by using clean water after the calibration is finished, readjusting the pH value of the solution until the pH value is in the normal range, then adjusting the pH value of the plating solution to be between 9 and 9.5 by using ammonia water, and determining the pH value according to the initial pH value of the solution.
(4) Putting micro/nano lignocellulose prepared by ultrasonic as a sample into an activating solution A for activating for 15 minutes, uniformly stirring by using a glass rod, stirring 1 time by using the glass rod every 2 minutes, filtering 2 times by using a double-layer filter screen, taking out the sample, putting the sample into an activating solution B for activating till no liquid drips, wherein the activating time is 90 seconds, uniformly stirring by using the glass rod, stirring 1 time by using the glass rod every 30 seconds, filtering 2 times by using the double-layer filter screen, filtering the sample by adopting a back-and-forth snowball rolling mode, at the moment, the surface of the sample becomes black, releasing air bubbles between gaps, immediately reactivating the sample if the surface of the sample does not become black, releasing the air bubbles between the gaps, till the phenomenon is normal, then taking out till no activating solution drips on the surface, putting the sample into a chemical plating solution, keeping the pH value at 9-9.5, and plating nickel for 30 minutes at the temperature of 60 ℃, and after 30 minutes, reconfiguring the plating solution and continuously carrying out chemical nickel plating, after carrying out nickel plating treatment for 2 times, filtering for 2 times by adopting a double-layer filter screen, placing the sample on the surface of a dry wood chip with the length and the width of 8cm and the x of 3cm for drying treatment, filtering the dried sample for 2 times by adopting the double-layer filter screen, uniformly shaking the filter screen to obtain the metallized cellulose with uniform appearance and appearance, and storing the sample.
(5) Taking prepared metallized cellulose as a precursor, stirring at high speed by an electric stirrer, weighing 0.1g of metallized cellulose, dispersing the metallized cellulose into a mixed solution of 45mL of ethanol and 0.5mL of TBOT (tetrabutyl titanate), stirring for 30 minutes, shaking the conical flask every 3 minutes, placing the uniformly stirred mixed solution into a water bath kettle with the water temperature of 95 ℃ to completely volatilize ethanol, converting the mixed solution into a cracked white flaky material and spreading the cracked white flaky material on the bottom of the whole conical flask, finally placing the dried powder into an FSX2-12-15N type muffle furnace to calcine at 600 ℃ for 6 hours, setting the muffle furnace for 3 time periods, preheating at 600 ℃ for 30min, heating at 600 ℃ for 6 hours, preserving the heat at 600 ℃ for 2 hours to obtain Ni-GO/NiO/TiO-TiO2A magnetic porous cylindrical structure.
Example 3: TiO 22The preparation method of the basic magnetic porous composite material comprises the following specific steps:
(1) 0.6g of lignocellulose is weighed by an electronic balance, 300mL of distilled water is measured by a 500mL beaker, the weighed lignocellulose is dissolved in the distilled water, and the mixture is uniformly stirred by a glass rod until the beaker forms a uniform suspension.
(2) The SM-1200D ultrasonic signal generator is used for dispersing lignocellulose, and three points need to be paid attention to the adjustment of the amplitude transformer: 1. the amplitude transformer is placed at a half position of the height of the solution, 2, the amplitude transformer is positioned at the center of the circle of the solution, and 3, the amplitude transformer does not approach the temperature control sensor; the dispersion time is 180 minutes, the power is 960W, the beaker with the lignocellulose dissolved is placed in a device for placing ice blocks, the ice blocks are continuously replaced in the period, the frequency of replacing the ice blocks is different according to seasons, the ice is replaced every 15 minutes in summer, the ice is replaced every 30 minutes in winter, and the temperature of the ultrasonic water bath is always kept at about 33 ℃.
(3) Three 500mL beakers were taken, 200mL of distilled water in the first beaker and labeled a, 200mL of distilled water in the second beaker and labeled B, and 310mL of distilled water in the third beaker and labeled C. Slowly pouring concentrated hydrochloric acid into the solution A, uniformly stirring the concentrated hydrochloric acid by using a glass rod, adding nickel sulfate, and uniformly stirring the mixture, wherein the concentration of the nickel sulfate is 0.75 mL/g. And slowly pouring sodium hydroxide into the beaker B, uniformly stirring by using a glass rod, adding sodium borohydride, and uniformly stirring, wherein the mass ratio of the sodium hydroxide to the sodium borohydride is 0.75: 0.95. Placing a glass C filled with 310mL of distilled water in a constant-temperature water bath kettle at 60 ℃ for preheating for 15 minutes, taking the actual solution ratio according to 310mL of distilled water as a standard, evaporating part of water mainly due to preheating, and measuring 9.2g of nickel sulfate, 8.5g of sodium citrate, 7.8g of sodium hypophosphite and 15mg of thiourea in sequence and stirring and dissolving uniformly in sequence if the solution concentration is not deviated. Carefully observing the pH value of the acidimeter before adjusting the pH value, wherein the normal range is between 5.2 and 5.8, if the pH value is not between 5.2 and 5.8, reconfiguring the plating solution or calibrating the acidimeter, calibrating the acidimeter by adopting 2 ways, firstly calibrating the acidimeter by using deionized water, then calibrating the acidimeter by using an alkaline solution with the pH value of 9.15, flushing the acidimeter by using clean water after the calibration is finished, readjusting the pH value of the solution until the pH value is in the normal range, then adjusting the pH value of the plating solution to be between 9 and 9.5 by using ammonia water, and determining the pH value according to the initial pH value of the solution.
(4) Putting micro/nano lignocellulose prepared by ultrasonic as a sample into an activating solution A for activating for 15 minutes, uniformly stirring by using a glass rod, stirring 1 time by using the glass rod every 2 minutes, filtering 2 times by using a double-layer filter screen, taking out the sample, putting the sample into an activating solution B for activating till no liquid drips, wherein the activating time is 90 seconds, uniformly stirring by using the glass rod, stirring 1 time by using the glass rod every 30 seconds, filtering 2 times by using the double-layer filter screen, filtering the sample by adopting a back-and-forth snowball rolling mode, at the moment, the surface of the sample becomes black, releasing air bubbles between gaps, immediately reactivating the sample if the surface of the sample does not become black, releasing the air bubbles between the gaps, till the phenomenon is normal, then taking out till no activating solution drips on the surface, putting the sample into a chemical plating solution, keeping the pH value at 9-9.5, and plating nickel for 30 minutes at the temperature of 60 ℃, and after 30 minutes, reconfiguring the plating solution and continuously carrying out chemical nickel plating, after carrying out nickel plating treatment for 2 times, filtering for 2 times by adopting a double-layer filter screen, placing the sample on the surface of a dry wood chip with the length and the width of 8cm and the x of 3cm for drying treatment, filtering the dried sample for 2 times by adopting the double-layer filter screen, uniformly shaking the filter screen to obtain the metallized cellulose with uniform appearance and appearance, and storing the sample.
(5) Taking prepared metallized cellulose as a precursor, stirring at high speed by an electric stirrer, weighing 0.12g of metallized cellulose, dispersing the metallized cellulose into a mixed solution of 47mL of ethanol and 0.7mL of tetrabutyl titanate in a conical flask, stirring for 30 minutes, shaking the conical flask every 3 minutes, placing the uniformly stirred mixed solution in a water bath kettle with the water temperature of 95 ℃ to completely volatilize the ethanol, converting the mixed solution into a cracked white flaky material and spreading the cracked white flaky material on the bottom of the whole conical flask, placing the dried powder in an FSX2-12-15N type muffle furnace to be calcined at 600 ℃ for 6 hours, setting the muffle furnace for 3 time periods, preheating at 600 ℃ for 30min, heating at 600 ℃ for 6 hours, preserving the heat at 600 ℃ for 2 hours to obtain Ni-NiO/TiO-GO-TiO-GO2A magnetic porous cylindrical structure.
Example 4: TiO 22The preparation method of the basic magnetic porous composite material comprises the following specific steps:
(1) 0.6g of lignocellulose is weighed by an electronic balance, 300mL of distilled water is measured by a 500mL beaker, the weighed lignocellulose is dissolved in the distilled water, and the mixture is uniformly stirred by a glass rod until the beaker forms a uniform suspension.
(2) The SM-1200D ultrasonic signal generator is used for dispersing lignocellulose, and three points need to be paid attention to the adjustment of the amplitude transformer: 1. the amplitude transformer is placed at a half position of the height of the solution, 2, the amplitude transformer is positioned at the center of the circle of the solution, and 3, the amplitude transformer does not approach the temperature control sensor; the dispersion time is 180 minutes, the power is 960W, the beaker with the lignocellulose dissolved is placed in a device for placing ice blocks, the ice blocks are continuously replaced in the period, the frequency of replacing the ice blocks is different according to seasons, the ice is replaced every 15 minutes in summer, the ice is replaced every 30 minutes in winter, and the temperature of the ultrasonic water bath is always kept at about 37 ℃.
(3) Three 500mL beakers were taken, 200mL of distilled water in the first beaker and labeled a, 200mL of distilled water in the second beaker and labeled B, and 310mL of distilled water in the third beaker and labeled C. Slowly pouring concentrated hydrochloric acid into the solution A, uniformly stirring the solution by using a glass rod, adding nickel sulfate, and uniformly stirring the solution to obtain a solution with the concentration of 0.85 mL/g. And slowly pouring sodium hydroxide into the beaker B, uniformly stirring by using a glass rod, adding sodium borohydride, and uniformly stirring, wherein the mass ratio of the sodium hydroxide to the sodium borohydride is 0.85: 1.0. Placing a glass C filled with 310mL of distilled water in a constant-temperature water bath kettle at 60 ℃ for preheating for 15 minutes, taking the actual solution ratio according to 310mL of distilled water as a standard, evaporating part of water mainly due to preheating, and measuring 11g of nickel sulfate, 9.5g of sodium citrate, 9g of sodium hypophosphite and 25mg of thiourea in sequence and stirring and dissolving the nickel sulfate, the sodium citrate, the sodium hypophosphite and the thiourea in sequence to be uniform. Carefully observing the pH value of the acidimeter before adjusting the pH value, wherein the normal range is between 5.2 and 5.8, if the pH value is not between 5.2 and 5.8, reconfiguring the plating solution or calibrating the acidimeter, calibrating the acidimeter by adopting 2 ways, firstly calibrating the acidimeter by using deionized water, then calibrating the acidimeter by using an alkaline solution with the pH value of 9.15, flushing the acidimeter by using clean water after the calibration is finished, readjusting the pH value of the solution until the pH value is in the normal range, then adjusting the pH value of the plating solution to be between 9 and 9.5 by using ammonia water, and determining the pH value according to the initial pH value of the solution.
(4) Putting micro/nano lignocellulose prepared by ultrasonic as a sample into an activating solution A for activating for 15 minutes, uniformly stirring by using a glass rod, stirring 1 time by using the glass rod every 2 minutes, filtering 2 times by using a double-layer filter screen, taking out the sample, putting the sample into an activating solution B for activating till no liquid drips, wherein the activating time is 90 seconds, uniformly stirring by using the glass rod, stirring 1 time by using the glass rod every 30 seconds, filtering 2 times by using the double-layer filter screen, filtering the sample by adopting a back-and-forth snowball rolling mode, at the moment, the surface of the sample becomes black, releasing air bubbles between gaps, immediately reactivating the sample if the surface of the sample does not become black, releasing the air bubbles between the gaps, till the phenomenon is normal, then taking out till no activating solution drips on the surface, putting the sample into a chemical plating solution, keeping the pH value at 9-9.5, and plating nickel for 30 minutes at the temperature of 60 ℃, and after 30 minutes, reconfiguring the plating solution and continuously carrying out chemical nickel plating, after carrying out nickel plating treatment for 2 times, filtering for 2 times by adopting a double-layer filter screen, placing the sample on the surface of a dry wood chip with the length and the width of 8cm and the x of 3cm for drying treatment, filtering the dried sample for 2 times by adopting the double-layer filter screen, uniformly shaking the filter screen to obtain the metallized cellulose with uniform appearance and appearance, and storing the sample.
(5) Taking prepared metallized cellulose as a precursor, stirring at high speed by an electric stirrer, weighing 0.14 g of metallized cellulose dispersed to a mixed solution of 53mL of ethanol and 1.3mL of TBOT (tetrabutyl titanate), stirring for 30 minutes, shaking the conical flask every 3 minutes, placing the uniformly stirred mixed solution in a water bath kettle with the water temperature of 95 ℃ to completely volatilize the ethanol, converting the mixed solution into a cracked white flaky material and spreading the cracked white flaky material on the bottom of the whole conical flask, finally placing the dried powder in an FSX2-12-15N type muffle furnace to be calcined at 600 ℃ for 6 hours, setting the muffle furnace for 3 time periods, preheating at 600 ℃ for 30min, heating at 600 ℃ for 6 hours, preserving the heat at 600 ℃ for 2 hours to obtain Ni-NiO/TiO-GO-TiO2A magnetic porous cylindrical structure.
Example 5: TiO 22The preparation method of the basic magnetic porous composite material comprises the following specific steps:
(1) 0.6g of lignocellulose is weighed by an electronic balance, 300mL of distilled water is measured by a 500mL beaker, the weighed lignocellulose is dissolved in the distilled water, and the mixture is uniformly stirred by a glass rod until the beaker forms a uniform suspension.
(2) The SM-1200D ultrasonic signal generator is used for dispersing lignocellulose, and three points need to be paid attention to the adjustment of the amplitude transformer: 1. the amplitude transformer is placed at a half position of the height of the solution, 2, the amplitude transformer is positioned at the center of the circle of the solution, and 3, the amplitude transformer does not approach the temperature control sensor; the dispersion time is 180 minutes, the power is 960W, the beaker with the lignocellulose dissolved is placed in a device for placing ice blocks, the ice blocks are continuously replaced in the period, the frequency of replacing the ice blocks is different according to seasons, the ice is replaced every 15 minutes in summer, the ice is replaced every 30 minutes in winter, and the temperature of the ultrasonic water bath is always kept at about 40 ℃.
(3) Three 500mL beakers were taken, 200mL of distilled water in the first beaker and labeled a, 200mL of distilled water in the second beaker and labeled B, and 310mL of distilled water in the third beaker and labeled C. Slowly pouring concentrated hydrochloric acid into the solution A, uniformly stirring the solution by using a glass rod, adding nickel sulfate, and uniformly stirring the solution to obtain a solution with the concentration of 0.9 mL/g. And slowly pouring sodium hydroxide into the beaker B, uniformly stirring by using a glass rod, adding sodium borohydride, and uniformly stirring, wherein the mass ratio of the sodium hydroxide to the sodium borohydride is 0.9: 1.1. Placing a glass C filled with 310mL of distilled water in a constant-temperature water bath kettle at 60 ℃ for preheating for 15 minutes, taking the actual solution ratio according to 310mL of distilled water as a standard, evaporating part of water mainly due to preheating, and measuring 12g of nickel sulfate, 10g of sodium citrate, 10g of sodium hypophosphite and 30mg of thiourea in sequence and stirring and dissolving uniformly in sequence if the solution concentration is not deviated. Carefully observing the pH value of the acidimeter before adjusting the pH value, wherein the normal range is between 5.2 and 5.8, if the pH value is not between 5.2 and 5.8, reconfiguring the plating solution or calibrating the acidimeter, calibrating the acidimeter by adopting 2 ways, firstly calibrating the acidimeter by using deionized water, then calibrating the acidimeter by using an alkaline solution with the pH value of 9.15, flushing the acidimeter by using clean water after the calibration is finished, readjusting the pH value of the solution until the pH value is in the normal range, then adjusting the pH value of the plating solution to be between 9 and 9.5 by using ammonia water, and determining the pH value according to the initial pH value of the solution.
(4) Putting micro/nano lignocellulose prepared by ultrasonic as a sample into an activating solution A for activating for 15 minutes, uniformly stirring by using a glass rod, stirring 1 time by using the glass rod every 2 minutes, filtering 2 times by using a double-layer filter screen, taking out the sample, putting the sample into an activating solution B for activating till no liquid drips, wherein the activating time is 90 seconds, uniformly stirring by using the glass rod, stirring 1 time by using the glass rod every 30 seconds, filtering 2 times by using the double-layer filter screen, filtering the sample by adopting a back-and-forth snowball rolling mode, at the moment, the surface of the sample becomes black, releasing air bubbles between gaps, immediately reactivating the sample if the surface of the sample does not become black, releasing the air bubbles between the gaps, till the phenomenon is normal, then taking out till no activating solution drips on the surface, putting the sample into a chemical plating solution, keeping the pH value at 9-9.5, and plating nickel for 30 minutes at the temperature of 60 ℃, and after 30 minutes, reconfiguring the plating solution and continuously carrying out chemical nickel plating, after carrying out nickel plating treatment for 2 times, filtering for 2 times by adopting a double-layer filter screen, placing the sample on the surface of a dry wood chip with the length and the width of 8cm and the x of 3cm for drying treatment, filtering the dried sample for 2 times by adopting the double-layer filter screen, uniformly shaking the filter screen to obtain the metallized cellulose with uniform appearance and appearance, and storing the sample.
(5) Taking prepared metallized cellulose as a precursor, stirring at high speed by an electric stirrer, weighing 0.15g of metallized cellulose, dispersing the metallized cellulose into a mixed solution of 55mL of ethanol and 1.5mL of tetrabutyl titanate in a conical flask, stirring for 30 minutes, shaking the conical flask every 3 minutes, placing the uniformly stirred mixed solution in a water bath kettle with the water temperature of 95 ℃ to completely volatilize the ethanol, converting the mixed solution into a cracked white flaky material and spreading the cracked white flaky material on the bottom of the whole conical flask, finally placing the dried powder in an FSX2-12-15N type muffle furnace to be calcined at 600 ℃ for 6 hours, setting the muffle furnace for 3 time periods, preheating at 600 ℃ for 30min, heating at 600 ℃ for 6 hours, preserving the heat at 600 ℃ for 2 hours to obtain Ni-NiO/TiO-GO-TiO-GO2A magnetic porous cylindrical structure.
Ni-NiO/GO-TiO2Magnetic porous cylindrical structure formation mechanism: peeling the lignocellulose cell wall, wherein a large number of pore structures appear on the surface of the lignocellulose cell wall, so that the porous nano lignocellulose is prepared; based on a multi-time chemical Ni plating method, carrying out 1-time chemical Ni plating and 2-time chemical Ni plating on the surface of the nano lignocellulose, adding nano graphene in the 2 nd-time chemical Ni plating process, and coating a metal layer on the surface of the porous nano lignocellulose to form a magnetic cylindrical structure; then, compounding the cylindrical structure, tetrabutyl titanate (TBOT) and nano-graphene by means of a sol-gel method, stirring continuously in the compounding process to enable the cylindrical structure, the tetrabutyl titanate (TBOT) and the nano-graphene to be compounded uniformly, calcining the composite structure at high temperature, so that the composite coating coated on the surface pore structure can collapse, and finally, the cylindrical structure and the nano-TiO are formed2Realizes uniform composition with nano-graphene, successfully prepares Ni-NiO/GO-TiO2The light reflection schematic diagram of the magnetic porous cylindrical structure is shown in figure 2.
Claims (1)
1. TiO 22The preparation method of the basic magnetic porous composite material is characterized in that the composite material takes nano lignocellulose as a framework and porous Ni-NiO/GO-TiO on the surface2A composite cylindrical structure;
the method comprises the following steps:
step 1, weighing lignocellulose, dissolving the lignocellulose in deionized water, and uniformly stirring the lignocellulose until uniform suspension is formed;
step 2, dispersing lignocellulose by using an ultrasonic signal generator; the dispersion time is 180 minutes, the power is 960W, the ultrasonic water bath temperature is 30-40 ℃, and the climate environment influences the temperature setting;
step 3, preparing an activating solution A, an activating solution B and a chemical plating solution C, wherein the activating solution A is a mixed solution of concentrated hydrochloric acid and nickel sulfate, and the concentration of the mixed solution is 0.8 mL/g; the activating solution B is a mixed solution of sodium hydroxide and sodium borohydride, and the mass ratio of the activating solution B to the sodium borohydride is 0.8: 1; and the solution C is a mixed plating solution of nickel sulfate, sodium citrate, sodium hypophosphite and thiourea, and the mass ratio of the plating solution C is nickel sulfate: sodium citrate: sodium hypophosphite: thiourea 9.9: 9: 8.4: 0.02;
step 4, taking the nano lignocellulose prepared in the step 2 as a sample, putting the sample into an activating solution A for activation, filtering the sample, taking the sample out, putting the sample into an activating solution B for activation, taking the sample out after the activation is successful, putting the sample into a chemical plating solution C for nickel plating, preparing the chemical plating solution again according to laboratory conditions for specific chemical plating time, continuously performing chemical nickel plating, adding nano graphene in the second chemical nickel plating process, performing nickel plating for 2 times, filtering the sample for 2 times, drying the sample, filtering the dried sample for 2 times, obtaining metallized cellulose with uniform appearance, and storing the sample;
and 5, taking the metallized cellulose prepared in the step 4 as a precursor, and weighing 0.1-0.15g of metallized cellulose to disperse into ethanol in a volume ratio of: mixing tetrabutyl titanate TBOT 50:1 with ethanol and TBOT, stirring, placing in water bath to completely volatilize ethanol, and spreading the mixture to the bottom of the containerThen placing the dried powder in a muffle furnace for calcining to obtain Ni-NiO/GO-TiO2A magnetic porous cylindrical composite material;
in the step 5, the muffle furnace is FSX2-12-15N in model, calcining is carried out for 6 hours at 600 ℃, the muffle furnace is set for 3 time periods, preheating is carried out for 30min at 600 ℃, heating is carried out for 6 hours at 600 ℃, heat preservation is carried out for 2 hours at 600 ℃, and finally Ni-NiO/GO-TiO is obtained2A magnetic porous cylindrical composite material;
in the step 3, the pH value of the chemical plating solution C is 9-9.5; measuring pH value with acidity meter before adjusting pH value, wherein the normal range is 5.2-5.8, and if pH value is not within 5.2-5.8, preparing plating solution again or calibrating acidity meter; calibrating the acidimeter by using deionized water, then calibrating by using an alkaline solution with the pH value of 9.15, washing the acidimeter by using clear water after the calibration is finished, readjusting the pH value of the solution to be in a normal range, then adjusting the pH value of the plating solution to be 9-9.5 by using ammonia water, determining the final pH value of the plating solution according to the pH value of the initially prepared plating solution, and adjusting the pH value of the plating solution to be in a range of 9-9.5;
step 1, weighing by using an electronic balance;
in the step 2, an amplitude transformer of the ultrasonic signal generator is placed at a half position of the height of the solution, the amplitude transformer is positioned at the center of the circle of the solution, and the amplitude transformer is far away from a temperature control sensor of the ultrasonic signal generator;
in step 2, in the ultrasonic water bath process, the container dissolved with lignocellulose is placed in a device for placing ice cubes, the ice cubes are continuously replaced in the process, and the frequency of replacing the ice cubes is as follows: changing every 15 minutes in summer and every 30 minutes in winter; the temperature of the ultrasonic water bath is about 35 ℃;
step 4, the nano lignocellulose prepared in the step 2 is used as a sample, the sample is put into an activation solution A for activation for 15 minutes and is uniformly stirred, the sample is stirred for 1 time every 2 minutes and is filtered for 2 times by a double-layer filter screen, the sample is taken out and is put into a solution B for activation till no liquid drips, the activation time is 90 seconds, the sample is uniformly stirred and is stirred for 1 time every 30 seconds, the sample is filtered for 2 times by the double-layer filter screen, the sample is filtered by a back-and-forth snowball rolling mode, the sample is taken out after the activation is successful, when no liquid drips on the surface, the sample is put into a chemical plating solution C, the pH value is 9-9.5, the nickel is plated for 25-35 minutes under the condition of 60 ℃, the specific chemical plating time is according to laboratory conditions, then the chemical plating solution is prepared again and chemical nickel is continuously plated, the sample is filtered for 2 times by the double-layer filter screen after the 2 times of nickel plating, the sample is dried, the, uniformly shaking the filter screen to obtain metallized cellulose with uniform appearance and appearance, and storing a sample;
step 5, mixing the metal cellulose, ethanol and TBOT (tetrabutyl titanate) under high-speed stirring for 25-30 minutes, shaking the container every 2-5 minutes, and then placing the uniformly stirred mixed solution into a water bath with the water temperature of 95 ℃ for reaction to obtain a white flaky material;
in step 4, the successful activation is marked by the following phenomena: and if the sample does not have the mark phenomenon of successful activation, the sample is immediately reactivated until the mark phenomenon of successful activation appears.
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| CN104084186A (en) * | 2014-07-23 | 2014-10-08 | 武汉理工大学 | Graphene/titanium dioxide photocatalysis composite material and preparation method thereof |
| CN104226253A (en) * | 2014-10-13 | 2014-12-24 | 武汉大学 | Graphene oxide-TiO2 composite material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104226253A (en) * | 2014-10-13 | 2014-12-24 | 武汉大学 | Graphene oxide-TiO2 composite material and preparation method and application thereof |
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| Title |
|---|
| "木质纤维素基磁性中空复合材料的制备及其性能研究";潘艳飞;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20170215(第2期);B020-87，摘要、第13-14、25-26、33-34、47-48、55、59-62、109-114页 * |
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